Novel tetrazolinone derivatives

ABSTRACT

The invention relates to novel tetrazolinone derivatives of general formula (I) wherein R 1  represents halogen, C 1-4  alkyl, C 1-4  haloalkyl, C 1-4  alkoxy, C 1-4  alkylthio, C 1-4  alkylsulfonyl, C 1-4  alkylsulfonyloxy, C 2-5  alkoxycarbonyl. C 2-6  alkoxyalkyl, C 2-6  alkylthioalkyl, nitro or cyano, R 2  represents a hydrogen atom, C 1-4  alkyl, C 3-6  cycloalkyl which may be optionally substituted with halogen or C 1-3  alkyl, C 1-4  haloalkyl, or phenyl which may be optionally substituted with halogen, C 1-3  alkyl, C 1-3  haloalkyl or nitro, m represents 0.1 or 2, n represents 0 or 1, Q represents one of the groups which are mentioned in the description. The invention further relates to their use as herbicides and a process together with the intermediates for their preparation.

[0001] The present invention relates to novel tetrazolinone derivatives,to processes for their preparation and to their use as herbicides.

[0002] It has already been known that certain kinds of tetrazolederivatives show herbicidal activity (Japanese Laid-open PatentApplication Nos. 12275/1999 and 21280/1999). Moreover, it has furtheralready been known, that certain kinds of heterocyclic derivatives alsoshow herbicidal activity (U.S. Pat. Nos. 5,834,402 and 5,846,906)

[0003] There have now been found novel tetrazolinone derivatives of thegeneral formula (I)

[0004] wherein

[0005] R¹ represents halogen, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy,C₁₋₄ alkylthio, C₁₋₄ alkylsulfonyl, C₁₋₄ alkylsulfonyloxy, C₂₋₅alkoxycarbonyl, C₂₋₆ alkoxyalkyl, C₂₋₆ alkylthioalkyl, nitro or cyano,

[0006] R² represents a hydrogen atom, C₁₋₆ alkyl, C₃₋₆ cycloalkyl whichmay be optionally substituted with halogen or C₁₋₃ alkyl, C₁₋₄haloalkyl, or phenyl which may be optionally substituted with halogen,C₁₋₃ alkyl, C₁₋₃ haloalkyl or nitro,

[0007] m represents 0, 1 or 2; while the two R¹ substituents may beidentical or different, in case m represents 2,

[0008] n represents 0 or 1, and

[0009] Q represents one of the following groups

[0010] in which

[0011] R³, R⁴, R⁵, R⁶, R⁷ and R⁸ each independently represent a hydrogenatom or C₁₋₄ alkyl,

[0012] or

[0013] R³ and R⁸ may form an ethylene chain together,

[0014] R⁹ represents C₁₋₄ alkyl,

[0015] R¹⁰ represents C₁₋₄ alkyl or C₃₋₆ cycloalkyl which may beoptionally substituted with methyl.

[0016] The compounds of the general formula (I), according to theinvention, can be obtained by a process in which

[0017] a) compounds of the general formula (IIa)

[0018] wherein

[0019] R¹, R², m and n have the same definition as aforementioned, and

[0020] T¹ represents one of the following groups

[0021] in which

[0022] R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ have the same definition asmentioned above,

[0023] are reacted to a rearrangement in the presence of a base and acyanide,

[0024] or

[0025] b) in case that Q represents group (Q-2):

[0026] compounds of the general formula (IIb)

[0027] wherein

[0028] R¹, R², m and n have the same definitions as mentioned above, and

[0029] T² represents one of the following groups;

[0030] in which

[0031] R⁹ has the same definition as mentioned above,

[0032] are reacted to a rearrangement in the presence of a base,

[0033] or

[0034] c) in case that Q represents group (Q-3):

[0035] compounds of the general formula (III)

[0036] wherein

[0037] R¹, R², R¹⁰, m and n have the same definitions as mentionedabove, and

[0038] R¹¹ represents C₁₋₄ alkyl, preferably methyl or ethyl,

[0039] are reacted with hydroxylamine,

[0040] or

[0041] d) in case that Q represents group (Q-4):

[0042] compounds of the general formula (Ib)

[0043] wherein

[0044] R¹, R², R¹⁰, m and n have the same definition as mentioned above,

[0045] are reacted to a ring-opening in the presence of a base.

[0046] The tetrazolinone derivatives of the general formula (I) providedby the present invention show a superior herbicidal activity comparedwith the compounds described in the aforementioned prior artliteratures.

[0047] In the general formulae:

[0048] “Halogen” represents fluoro, chloro, bromo or iodo, andpreferably represents fluoro, chloro or bromo.

[0049] “Alkyl” may be straight or branched chain and there may bementioned, for example, C₁₋₆ alkyl, specifically methyl, ethyl, n- oriso-propyl, n-, iso-, sec- or tert-butyl, n-, iso-, neo-, ortert-pentyl, n- or iso-hexyl.

[0050] As “cycloalkyl” there can be mentioned, for example, cyclopropyl,cyclobutyl, cyclopentyl or cyclohexyl. These cycloalkyls may beoptionally substituted with halogen (for example, fluorine, chlorine orbromine), C₁₋₃ alkyl (for example, methyl, ethyl, n- or iso-propyl) andin case a plurality of substituents exist, they may be identical ordifferent.

[0051] As specific examples of such substituted cycloalkyls there can bementioned 1-methylcyclopropyl, 1-ethylcyclopropyl,1-n-propylcyclopropyl, 1-methyl-2-fluorocyclopropyl,2-methylcyclopropyl, 2-fluorocyclopropyl,1-methyl-2,2-difluorocyclopropyl, 1-methyl-2,2-dichlorocyclopropyl,2,2-difluorocyclopropyl, 2-methylcyclopentyl, 1-methylcyclohexyl,2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl,2,3-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 2,5-dimethylcyclohexyl.

[0052] “Haloalkyl” represents straight or branched chain alkyl, of whichat least one hydrogen is substituted with halogen, and there may bementioned, for example, C₁₋₄ alkyl substituted with 1 to 6 fluorineatoms and/or chlorine atoms, and more specifically for exampledifluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, dichloromethyl,2-chloro-1,1,2-trifluoroethyl, 3-fluoropropyl, 3-chloropropyl,2,2,3,3,3-pentafluoropropyl or 1,2,2,3,3,3-hexafluoropropyl.

[0053] “Alkoxy” represents an —O-alkyl group, of which the alkyl parthas the above-mentioned meaning. “Alkoxy” and can be, for example, C₁₋₄alkoxy, and more specifically for example methoxy, ethoxy, n- oriso-propoxy, n-, iso-, sec- or tert-butoxy.

[0054] “Alkylthio” represents an —S-alkyl group, of which the alkyl parthas the above-mentioned meaning. “Alkylthio” can be, for example, C₁₋₄alkylthio, and more specifically for example methylthio, ethylthio, n-or iso-propylthio, n-, iso-, sec- or tert-butylthio.

[0055] “Alkylsulfonyl” represents a —SO₂-alkyl group, of which the alkylpart has the above-mentioned meaning. “Alkylsulfonyl” can be, forexample, C₁₋₄ alkylsulfonyl, and more specifically for examplemethylsulfonyl, ethylsulfonyl, n- or iso-propylsulfonyl, n-, iso-, sec-or tert-butylsulfonyl.

[0056] “Alkylsulfonyloxy” represents a —O—SO₂-alkyl group, of which thealkyl part has the above-mentioned meaning. “Alkylsulfonyloxy” can be,for example, C₁₋₄ alkyl-sulfonyloxy, and more specifically for examplemethylsulfonyloxy, ethylsulfonyloxy, n- or iso-propylsulfonyloxy, n-,iso-, sec- or tert-butylsulfonyloxy.

[0057] “Alkoxycarbonyl” represents a —CO—O-alkyl group, of which thealkyl part has the above-mentioned meaning. “Alkoxycarbonyl” can be, forexample, C₂₋₅ alkoxy-carbonyl, and more specifically for examplemethoxycarbonyl, ethoxycarbonyl, n- or iso-propoxycarbonyl, n-, iso-,sec- or tert-butoxycarbonyl.

[0058] “Alkoxyalkyl” represents alkyl substituted with alkoxy and canbe, for example, C₂₋₆ alkoxyalkyl, and more specifically for examplemethoxymethyl, 1-methoxyethyl, 2-methoxyethyl, 2-methoxy-1-methylethyl,methoxypropyl, methoxybutyl, methoxy-pentyl, ethoxymethyl, n- oriso-propoxymethyl, n-, iso-, sec- or tert-butoxymethyl.

[0059] “Alkylthioalkyl” represents alkyl substituted with alkylthio andcan be, for example, C₂₋₆ alkylthioalkyl, and more specifically forexample methylthiomethyl, methyl-thioethyl, 1-methylthiopropyl,2-methylthiopropyl, 1-methyl-2-methylthioethyl, methylthiobutyl,methylthiopentyl, ethylthiomethyl, n- or iso-propylthiomethyl, n-, iso-,sec- or tert-butylthiomethyl.

[0060] As a preferred group of compounds of the present invention therecan be mentioned the compounds of the aforementioned general formula (I)wherein

[0061] R¹ represents fluoro, chloro, bromo, methyl, ethyl, C₁₋₂haloalkyl, methoxy, ethoxy, methylthio, ethylthio, methylsulfonyl,ethylsulfonyl, methyl-sulfonyloxy, ethylsulfonyloxy, methoxycarbonyl,ethoxycarbonyl, C₂₋₄ alkoxyalkyl, C₂₋₄ alkylthioalkyl, nitro or cyano,

[0062] R² represents a hydrogen atom, C₁₋₄ alkyl, C₃₋₅ cycloalkyl whichmay be optionally substituted with fluoro, chloro, bromo or C₁₋₃ alkyl,C₁₋₃ haloalkyl, or phenyl which may be optionally substituted withfluoro, chloro, bromo, methyl, ethyl, difluoromethyl or trifluoromethyl,

[0063] m represents 0, 1 or 2, while the two R¹ substituents may beidentical or different, in case m represents 2,

[0064] n represents 0 or 1, and

[0065] Q represents one of the following groups

[0066] or

[0067] wherein

[0068] R³, R⁴, R⁵, R⁶, R⁷ and R⁸ each independently represent a hydrogenatom, methyl or ethyl, and

[0069] R³ and R⁸ may form an ethylene chain together,

[0070] R⁹ represents C₁₋₃ alkyl,

[0071] R¹⁰ represents tert-butyl or cyclopropyl which may be optionallysubstituted with methyl.

[0072] As a more preferable group of compounds there can be mentionedthe compounds of the aforementioned general formula (I) wherein

[0073] R¹ represents chloro, bromo, methyl, trifluoromethyl, methoxy,methylthio, methylsulfonyl, methylsulfonyloxy, methoxycarbonyl,methoxymethyl, methylthiomethyl or nitro,

[0074] R² represents a hydrogen atom, methyl, ethyl, n-propyl,isopropyl, tert-butyl, cyclopropyl which may be optionally substitutedwith fluoro, chloro, methyl, ethyl or n-propyl, difluoromethyl,2,2,2-trifluoroethyl, 3-fluoropropyl, 2,2,3,3,3-pentafluoropropyl, orphenyl which may be optionally substituted with fluoro, chloro, methyl,difluoromethyl or trifluoromethyl,

[0075] m represents 0, 1 or 2, while two two R¹ substituents may beidentical or different, in case m represents 2,

[0076] n represents 0 or 1, and

[0077] Q represents one of the following groups

[0078] wherein

[0079] R⁹ represents methyl or ethyl,

[0080] R¹⁰ represents tert-butyl, cyclopropyl or 1-methylcyclopropyl.

[0081] The aforementioned preparation process a) is illustrated by thefollowing reaction scheme for the case that for example,3-oxo-1-cyclohexenyl2,4-dichloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoate isused as the starting material.

[0082] The aforementioned preparation process b) is illustrated by thefollowing reaction scheme for the case that, for example,5-[2,4-dichloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoyloxy]-1-ethylpyrazoleor1-[2,4-dichloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoyl]-2-ethyl-2,3-dihydro-1H-3-pyrazoloneare used as the starting material.

[0083] The aforementioned preparation process c) is illustrated by thefollowing reaction for the case that, for example,3-cyclopropyl-1-{3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2,4-dichlorophenyl}-2-ethoxymethylenepropane-1,3-dioneand hydroxylamine is used as the starting material.

[0084] The aforementioned preparation process d) is illustrated by thefollowing reaction scheme for the case that, for example,5-cyclopropyl-4-{3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2,4-dichlorobenzoyl}isoxazoleis used as the starting material.

[0085] The compounds of the general formula (IIa), the starting materialin the above-mentioned preparation process a) are novel compounds whichwere not described in the literature before the date of application ofthe present application and can be prepared according to the processdescribed in the literature, for example, Japanese Laid-open PatentApplication Nos. 222/1990, 173/1990 and 6425/1990 by reacting compoundsof the general formula (IV)

[0086] wherein

[0087] R¹, R², m and n have the same definition as mentioned above, and

[0088] M represents halogen,

[0089] with compounds of the general formula (V)

Q¹-H   (V)

[0090] wherein

[0091] Q¹ represents the following group

[0092] or the group

[0093] in which

[0094] R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ have the same definition asmentioned above,

[0095] in an appropriate diluent, for example, dichloromethane, in thepresence of an appropriate condensing agent, for example, triethylamine.

[0096] The compounds represented by the above-mentioned general formula(IV) are also novel compounds which were not described in the literaturebefore the date of application of the present application and can beprepared, for example, by reacting compounds of the general formula (VI)

[0097] wherein

[0098] R¹, R², m and n have the same definition as mentioned above,

[0099] with a halogenating agent, for example, phosphorous oxychloride,phosphorous oxybromide, phosphorous trichloride, phosphorous tribromide,phosgene, carbonyl bromide, oxalyl dichloride, thionyl chloride, thionylbromide.

[0100] The compounds of the above-mentioned general formula (V) arecommercially available or can be easily prepared according to theprocesses described in the literature, for example, Japanese Laid-openPatent Application Nos. 6425/1990, 265415/1998, 265441/1998, and257974/1986.

[0101] The compounds of the above-mentioned general formula (VI) arealso novel compounds which were not described in the literature beforethe date of application of the present application and can be prepared,for example, by hydrolyzing compounds of the general formula (VII)

[0102] wherein

[0103] R¹, R², m and n have the same definition as mentioned above, and

[0104] R¹¹ represents C₁₋₄ alkyl, preferably methyl or ethyl,

[0105] in an appropriate diluent, for example, aqueous dioxane, in thepresence of an appropriate base, for example, sodium hydroxide.

[0106] The compounds of the above-mentioned general formula (VII) arealso novel compounds and the compounds, in case that n represents 0 inthe general formula (VII), can be easily obtained, for example, byreacting compounds of the general formula (VII)

[0107] wherein

[0108] R¹ and m have the same definition as mentioned above, and

[0109] R¹¹ represents C₁₋₄ alkyl, preferably methyl or ethyl,

[0110] with compounds of the general formula (IX)

R²-M   (IX)

[0111] wherein

[0112] R² has the same definition as mentioned above, and

[0113] M represents halogen,

[0114] in an appropriate diluent, for example, N,N-dimethylformamide, inthe presence of an appropriate condensing agent, for example, potassiumcarbonate.

[0115] The compounds of the above-mentioned general formula (VIII) arenovel compounds which were not described in the literature before thedate of application of the present application and can be easilyprepared according to the process described in the literature, forexample, Journal of Organic Chemistry, Vol. 45, 5130-5136 (1980),Journal of the American Chemical Society, Vol. 81, 3076-3079 (1959),Journal of the American Chemical Society, Vol. 72, 1888 (1950) byreacting the isocyanic acid esters derived from compounds of the generalformula (X)

[0116] wherein

[0117] R¹ and m have the same definition as mentioned above, and

[0118] R¹¹ represents C₁₋₄ alkyl, preferably methyl or ethyl,

[0119] with, for example, trimethylsilyl azide or sodium azide.

[0120] The compounds of the above-mentioned general formula (IX) areknown and commercially available.

[0121] The compounds of the above-mentioned general formula (X) are alsoknown and can be easily prepared according to the process described, forexample, in Japanese Laid-open Patent Application No. 173/1990.

[0122] Further, the compounds of the above-mentioned general formula(VII), in case that n represents 1, can be easily obtained, for example,by reacting compounds of the general formula (XI)

[0123] wherein

[0124] R² has the same definition as mentioned above,

[0125] with compounds of the general formula (XII)

[0126] wherein

[0127] R¹ and m have the same definition as mentioned above,

[0128] R¹¹ represents C₁₋₄ alkyl, preferably methyl or ethyl, and

[0129] M represents halogen,

[0130] in an appropriate diluent, for example, N,N-dimethylformamide, inthe presence of an appropriate condensing agent, for example, potassiumcarbonate.

[0131] The compounds of the above-mentioned general formula (XI) areknown compounds described, for example, in Japanese Laid-open PatentApplication Nos. 97372/1995 and 134045/1996 and can be, easily preparedaccording to the process described in the same references.

[0132] The compounds of the above-mentioned general formula (XII), asub-group of which are novel compounds which were not described in theliterature until now, can be easily prepared according to the processdescribed, for example, in Japanese Laid-open Patent Application No.173/1990.

[0133] Furthermore, the compounds of the general formula (IIa), startingmaterial in the above-mentioned preparation process a), can be easilyprepared from compounds of the general formula (VI) according to theprocess described, for example, in WO93/1803 1.

[0134] As typical examples of the compounds of the general formula(IIa), which are used as the starting material in the above-mentionedpreparation process a), the following can be mentioned:

[0135] 3-Oxo-1-cyclohexenyl2-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoate,3-oxo-1-cyclohexenyl2-[(4,5-diydro-4-methyl-5oxo-1H-tetrazol-1-yl)methyl]benzoate,

[0136] 3-oxo-1-cyclohexenyl2-[(4-cyclohexyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)-methyl]-4-fluorobenzoate,

[0137] 3-oxo-1-cyclohexenyl4-chloro-2-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoate,

[0138] 3-oxo-1-cyclohexenyl4-chloro-2-[(4,5-dihydro-4-ethyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoate,

[0139] 3-oxo-1-cyclohexenyl4-chloro-2-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]benzoate,

[0140] 3-oxo-1-cyclohexenyl4-bromo-2-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoate,

[0141] 3-oxo-1-cyclohexenyl2-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-4-trifluoromethylbenzoate,

[0142] 3-oxo-1-cyclohexenyl2-(4,5-dihydro-4-ethyl-5-oxo-1H-tetrazol-1-yl)-4-trifluoromethylbenzoate,

[0143] 3-oxo-1-cyclohexenyl2-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-4-nitrobenzoate,

[0144] 3-oxo-1-cyclohexenyl2-(4-difluoromethyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)-4-nitrobenzoate,

[0145] 3-oxo-1-cyclohexenyl2-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-4-nitrobenzoate,

[0146] 3-oxo-1-cyclohexenyl2-[(4,5-dihydro-4-phenyl-5-oxo-1H-tetrazol-1-yl)methyl]-4-nitrobenzoate,

[0147] 3-oxo-1-cyclohexenyl2-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-4-methylbenzoate,

[0148] 3-oxo-1-cyclohexenyl4-chloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-benzoate,

[0149] 3-oxo-1-cyclohexenyl2-chloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-benzoate,

[0150] 3-oxo-1-cyclohexenyl4-chloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-2-fluorobenzoate,

[0151] 3-oxo-1-cyclohexenyl2,4-dichloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-benzoate,

[0152] 3-oxo-1-cyclohexenyl2,4-dichloro-3-[4,5-dihydro-4-(3-fluoropropyl)-5-oxo-1H-tetrazol-1-yl]benzoate,

[0153] 3-oxo-1-cyclohexenyl2,4-dichloro-3-[4-(n-butyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl]benzoate,

[0154] 3-oxo-1-cyclohexenyl2,4-dichloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoate,

[0155] 3-oxo-1-cyclohexenyl2,4-dichloro-3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]benzoate,

[0156] 3-oxo-1-cyclohexenyl2,4-dichloro-3-{[4-(4-bromophenyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl]methyl}benzoate,

[0157] 3-oxo-1-cyclohexenyl2-chloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-4-methylsulfonylbenzoate,

[0158] 3-oxo-1-cyclohexenyl2-chloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-4-methylsulfonylbenzoate,

[0159] 3-oxo-1-cyclohexenyl2-chloro-3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-4-methylsulfonylbenzoate,

[0160] 3-oxo-1-cyclohexenyl2-chloro-3-{([4,5-dihydro-4-(n-pentyl)-5-oxo-1H-tetrazol-1-yl]methyl}-4-methylsulfonylbenzoate,

[0161] 3-oxo-1-cyclohexenyl2-chloro-3-{[4-(3-difluoromethylphenyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl]methyl)-4-methylsulfonylbenzoate,

[0162] 3-oxo-1-cyclohexenyl4-chloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-2-methylthiobenzoate,

[0163] 3-oxo-1-cyclohexenyl4-chloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-2-methylthiobenzoate,

[0164] 3-oxo-1-cyclohexenyl2,4-di(methylthio)-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoate,

[0165] 3-oxo-1-cyclohexenyl4-chloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-2-methylsulfonylbenzoate,

[0166] 3-oxo-1-cyclohexenyl4-chloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-methyl]-2-methylsulfonylbenzoate,

[0167] 3-oxo-1-cyclohexenyl4-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-3-methoxy-benzoate,

[0168] 3-oxo-1-cyclohexenyl2-chloro-4-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoate,

[0169] 3-oxo-1-cyclohexenyl2-chloro-4-(4,5-dihydro-4-isopropyl-5-oxo-1H-tetrazol-1-yl)benzoate,

[0170] 3-oxo-1-cyclohexenyl2-chloro-4-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoate,

[0171] 3-oxo-1-cyclohexenyl2-bromo-4-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoate,

[0172] 3-oxo-1-cyclohexenyl4-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-2-methoxybenzoate,

[0173] 3-oxo-1-cyclohexenyl4-{[4-(2-chlorophenyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl]methyl}-2-methoxybenzoate,

[0174] 3-oxo-1-cyclohexenyl4-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2-methylsulfonyloxybenzoate,

[0175] 3-oxo-1-cyclohexenyl4-(4,5dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-2-nitrobenzoate,

[0176] 3-oxo-1-cyclohexenyl4-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-2-nitrobenzoate,

[0177] 5,5-dimethyl-3-oxo-1-cyclohexenyl2-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-4-trifluoromethylbenzoate,

[0178] 5,5-dimethyl-3-oxo-1-cyclohexenyl2,4-dichloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoate,

[0179] 4,4-dimethyl-3-oxo-1-cyclohexenyl4-bromo-2-[(4,5-dihydromethyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoate,

[0180] 4,4-dimethyl-3-oxo-1-cyclohexenyl2,4-dichloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoate,

[0181]4-{4-chloro-2-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoyloxy}-bicyclo[3.2.1]-3-octen-2-one,

[0182]4-{2,4-dichloro-3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-benzoyloxybicyclo[3.2.1)-3-octen-2-one,

[0183]5-{(2-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-4-fluorobenzoyloxy}-1-methylpyrazole,

[0184]5-{4-bromo-2-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoyloxy}-1-ethylpyrazole,

[0185]5-{4-bromo-2-[(4,5-dihydro-4-ethyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoyloxy)-1-methylpyrazole,

[0186]5-{2-[(4,5-dihydro-4-(n-propyl)-5-oxo-1H-tetrazol-1-yl)methyl]-4-trifluoromethyl-benzoyloxy}-1-methylpyrazole,

[0187]5-[2-(4,5-dihydro4-methyl-5-oxo-1H-tetrazol-1-yl)4-methylbenzoyloxy]-1-ethyl-pyrazole,

[0188]5-[2-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)4-trifluoromethylbenzoyloxy]-1-ethylpyrazole,

[0189]5-[2,4-dichloro-3-(4,5-dihydro4-methyl-5-oxo-1H-tetrazol-1-yl)benzoyloxy]-1-ethylpyrazole,

[0190]5-{2,4-dichloro-3-{[4-(tert-butyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl}benzoyloxy}-1-ethylpyrazole,

[0191]5-[2-chloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-4-methylsulfonyl-benzoyloxy]-1-ethylpyrazole,

[0192]5-{2-chloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-4-methyl-sulfonylbenzoyloxy)-1-ethylpyrazole,

[0193]5-[4-chloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-2-methylthiobenzoyloxy]-1-ethylpyrazole,

[0194]5-{4-chloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-2-methylbenzoyloxy}-1-methylpyrazole,

[0195]5-{2,4-di(methylthio)-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-benzoyloxy}-1-ethylpyrazole,

[0196]5-[4-chloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-2-methylsulfonylbenzoyloxy]-1-ethylpyrazole,

[0197]5-{4-chloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-2-methylsulfonylbenzoyloxy}-1-ethylpyrazole,

[0198]5-[2-chloro-4-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoyloxy]-1-ethylpyrazole,

[0199]5-[2-chloro-4-(4-difluoromethyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)benzoyloxy]-1-methylpyrazole,

[0200]5-{2-chloro-4-[(4-cyclopropyl4,S-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]benzoyloxy}-1-ethylpyrazole,

[0201]5-[2-bromo4-(4,5-dihydro-4-ethyl-5-oxo-1H-tetrazol-1-yl)benzoyloxy]-1-methylpyrazole,

[0202]5-{4-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2-methoxybenzoyloxy}-1-ethylpyrazole,

[0203]5-{(4-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-2-methylsulfonyloxy-benzoyloxy}-1-ethylpyrazole,

[0204]5-[4-(4,5-dihydro4-methyl-5-oxo-1H-tetrazol-1-yl)-2-nitrobenzoyloxy]-1-methylpyrazole,

[0205]5-{4-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2-nitrobenzoyloxy)-1-ethylpyrazole.

[0206] The compounds of the general formula (IIb), the starting materialin the above-mentioned preparation process b), are a sub-group of thecompounds of the aforementioned general formula (IIa).

[0207] The compounds of the general formula (III), the starting materialin the above-mentioned preparation process c), are novel compounds,which were not described in the literature before the date ofapplication of the present application, and can be prepared according tothe process described, for example, in Japanese Laid-open PatentApplication No. 202008/1993 by reacting compounds of the general formula(XIII)

[0208] wherein

[0209] R¹, R², R¹⁰, m and n have the same definition as mentioned above,

[0210] with compounds of the general formula (XIV)

HC(OR¹¹)₃   (XIV)

[0211] wherein

[0212] R¹¹ has the same definition as aforementioned,

[0213] in an appropriate diluent, for example, acetic anhydride.

[0214] The compounds of the above-mentioned general formula (XIII) arenovel compounds, which were not described in the literature before thedate of application of the present application, and can be preparedaccording to the process described, for example, in Japanese Laid-openPatent Application No. 202008/1993 by reacting compounds of the generalformula (XV)

[0215] wherein

[0216] R¹, R², R¹⁰, m, n and R¹¹ have the same definition asaforementioned,

[0217] under an appropriate acidic condition in an appropriate diluent,for example, toluene in the presence of, for example, p-toluenesulfonicacid monohydrate.

[0218] The compounds of the above-mentioned general formula (XV) arenovel compounds, which were not described in the literature before thedate of application of the present application, and can be preparedaccording to the process described, for example, in Japanese Laid-openPatent Application No. 202008/1993 by reacting compounds of theabove-mentioned general formula (IV) with, for example, a complexobtained by treating compounds of the general formula (XVI)

[0219] wherein

[0220] R¹⁰ has the same definition as aforementioned,

[0221] R¹² represents C₁₋₄ alkyl,

[0222] with magnesium and carbon tetrachloride.

[0223] The compounds of the above-mentioned general formula (XVI) arecommercially available or can be prepared according to the processdescribed, for example, in Journal of Organic Chemistry, Vol. 43, 2087(1978).

[0224] The compounds of the above-mentioned general formula (XVI) arealready known.

[0225] As typical examples of the compounds of the general formula(III), which are used as the starting material in the above-mentionedpreparation process c), the following can be mentioned:

[0226]3-Cyclopropyl-1-{2-[(4,5-dihydro-4-ethyl-5-oxo-1H-tetrazol-1-yl)methyl]-4-fluorophenyl)-2-ethoxymethylenepropan-1,3-dione,

[0227]3-cyclopropyl-1-{(4-chloro-2-[(4,5-dihydro-4-ethyl-5-oxo-1H-tetrazol-1-yl)methylphenyl}-2-ethoxymethylenepropan-1,3-dione,

[0228]3-cyclopropyl-1-{2-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-4-trifluoromethylphenyl}-2-ethoxymethylenepropan-1,3-dione,

[0229]3-cyclopropyl-1-[2-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-4-trifluoromethylphenyl]-2-ethoxymethylenepropan-1,3-dione,

[0230]3-cyclopropyl-1-{4-chloro-3-[(4-cyclopropyl4,5-dihydro-5-oxo-1H-tetrazol-1-yl)-methyl]-2-fluorophenyl}-2-ethoxymethylenepropan-1,3-dione,

[0231]3-cyclopropyl-1-[2,4-dichloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)phenyl]-2-ethoxymethylenepropan-1,3-dione,

[0232]3-cyclopropyl-1-{3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2,4-dichlorophenyl}-2-ethoxymethylenepropan-1,3-dione,

[0233]3-cyclopropyl-1-{2-chloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-4-methylsulfonylphenyl}-2-ethoxymethylenepropan-1,3-dione,

[0234]3-cyclopropyl-1-[4-chloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-2-methylthiophenyl]-2-ethoxymethylenepropan-1,3-dione,

[0235]3-cyclopropyl-1-{4-chloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-2-methylsulfonylphenyl}-2-ethoxymethylenepropan-1,3-dione,

[0236]3-cyclopropyl-1-[2-chloro-4-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)phenyl]-2-ethoxymethylenepropan-1,3-dione,

[0237]3-(tert-butyl)-1-{2-chloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-4-methylsulfonylphenyl}-2-ethoxymethylenepropan-1,3-dione.

[0238] The compounds of the general formula (Ib), the starting materialin the above-mentioned preparation process d), are a sub-group of thecompounds of the general formula (I) of the present invention and can beeasily prepared according to the above-mentioned preparation process c).

[0239] As typical examples of the compounds of the general formula (Ib),which are used as the starting material in the above-mentionedpreparation process (d), there can be mentioned the following which areincluded in the general formula (I):

[0240]4-{4-Chloro-2-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl])benzoyl}-5-cyclopropylisoxazole,

[0241]5-cyclopropyl-4-[2-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)-4-nitrobenzoyl]-isoxazole,

[0242]4-{2-[(4-cyclohexyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-4-nitrobenzoyl}-5-cyclopropylisoxazole,

[0243]4-[2,4-dichloro-3-(4,5-dihydro-4methyl-5-oxo-1H-tetrazol-1-yl)benzoyl]-5-cyclopropylisoxazole,

[0244]4-{2,4-dichloro-3-[(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]benzoyl}-5-cyclopropylisoxazole,

[0245]4-{2-chloro-3-[(4,5-dihydro-4methyl-5-oxo-1H-tetrazol-1-yl)methyl]-4methyl-sulfonylbenzoyl)-5-cyclopropylisoxazole,

[0246]4-{4-chloro-3-[(4,5-dihydro4-methyl-5-oxo-1H-tetrazol-1-yl)methyl]-2-methylthiobenzoyl}-5-cyclopropylisoxazole,

[0247]4-[2chloro4-(4,5-dihydro4-methyl-5-oxo-1H-tetrazol-1-yl)benzoyl]-5-cyclopropylisoxazole.

[0248] The general formulae (IIa), (IIIb), (II), (IV), (VI), (VII),(VIII), (XIII) and (XV) of the novel starting materials andintermediates in the preparation processes of the compounds of theabove-mentioned general formula (I) of the present invention can berepresented collectively by the following general formula (XVII)

[0249] wherein

[0250] W represents T¹, M, hydroxy, or one of the following groups

[0251] OR¹¹,

[0252] in which

[0253] R¹, R², R¹⁰, R¹¹, m, n, T¹ and M have the same definition asmentioned above.

[0254] The reaction of the above-mentioned preparation process a) can beconducted in an appropriate diluent. As examples of such diluents usedin that case there can be mentioned aliphatic, alicydlic and aromatichydrocarbons (which may optionally be chlorinated), for example,toluene, dichloromethane, chloroform or 1,2-dichloroethane; ethers, forexample, ethyl ether, dimethoxyethane (DME) or tetrahydrofuran (THF);ketones, for example, methyl isobutyl ketone (MIBK); nitrites, forexample, acetonitrile; esters, for example, ethyl acetate; acid amides,for example, dimethyl-formamide (DMF).

[0255] The preparation process a) can be conducted in the presence of acyanide and a base. As a cyanide employable in that case there can bementioned, for example, sodium cyanide, potassium cyanide, acetonecyanohydrin or hydrogen cyanide. As a base there can be mentioned, forexample, as inorganic bases, hydroxides, carbonates etc. of alkalimetals and alkaline earth metals, for example, sodium carbonate,potassium carbonate, lithium hydroxide, sodium hydroxide, potassiumhydroxide or calcium hydroxide; and as organic bases, tertiary amines,dialkylaminoanilines and pyridines, for example, triethylamine,pyridine, 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo[2,2,2]octane(DABCO) or 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU).

[0256] The above-mentioned preparation process a) can be conducted alsoby adding a phase-transfer catalyst to the reaction mixture. As examplesof the phase-transfer catalyst employable in that case there can bementioned crown ethers, for example, dibenzo-18-crown-6, 18-crown-6,15-crown-5.

[0257] The preparation process a) can be conducted in a substantiallywide range of temperatures. Suitable temperatures are in the range ofgenerally about −10 to about 80° C., preferably about 5 to about 40° C.Said reaction is conducted desirably under normal pressure. Optionally,however, it is possible to conduct it under elevated pressure or underreduced pressure.

[0258] In conducting the preparation process a) the aimed compounds ofthe above-mentioned general formula (I), in case that Q representsgroups (Q-1) or (Q-2), can be obtained, for example, by reacting 1 moleof a compound of the general formula (II) with 1 to 4 moles oftriethylamine in a diluent, for example, acetonitrile, in the presenceof 0.01 to 0.5 moles of acetonecyanohydrin.

[0259] The reaction of the above-mentioned preparation process b) can beconducted in an appropriate diluent. As examples of such diluents usedin that case there can be mentioned ethers, for example, dioxane,tetrahydrofuran (THF); alcohols, for example, tert-amyl alcohol ortert-butyl alcohol.

[0260] The preparation process b) can be conducted in the presence of abase. As a base employable in that case there can be mentioned asinorganic bases, carbonates of alkali metals, for example, sodiumcarbonate or potassium carbonate; and as organic bases, tertiary amines,for example, triethylamine, pyridine or 4-dimethylamino-pyridine (DMAP).

[0261] The preparation process b) can be conducted in a substantiallywide range of temperatures. Suitable temperatures are in the range ofgenerally about 5 to about 200° C., preferably about 25 to about 130° C.Said reaction is conducted desirably under normal pressure. Optionally,however, it is possible to conduct it under elevated pressure or underreduced pressure.

[0262] In conducting the preparation process b) the aimed compounds ofthe aforementioned general formula (1), in case that Q represents group(Q-2), can be obtained by reacting 1 mole of a compound of the generalformula (II) with 0.5 to 2 moles of potassium carbonate in a diluent,for example, dioxane.

[0263] The reaction of the above-mentioned preparation process c) can beconducted in an appropriate diluent. As examples of such diluents usedin that case there can be mentioned aliphatic, alicyclic and aromatichydrocarbons (which may optionally be chlorinated), for example,toluene, dichloromethane, chloroform or 1,2-dichloroethane; ethers, forexample, tetrahydrofuran (THF); nitriles, for example, acetonitrile;alcohols, for example, methanol, ethanol or isopropanol.

[0264] The preparation process c) can be conducted in the presence of abase. As a base employable in that case there can be mentioned, asinorganic bases, acetates, carbonates, bicarbontes etc. of alkali metalsand alkaline earth metals, for example, sodium acetate, sodium hydrogencarbonate, potassium hydrogen carbonate, sodium carbonate or potassiumcarbonate; and as organic bases, tertiary amines, dialkyl-aminoanilinesand pyridines, for example, triethylamine, pyridine or4-di-methylaminopyridine (DMAP).

[0265] The preparation process c) can be conducted in a substantiallywide range of temperatures. Suitable temperatures are in the range ofgenerally about −10 to about 100° C., preferably about 0 to about 50 °C. Said reaction is conducted desirably under normal pressure.Optionally, however, it is possible to conduct it under elevatedpressure or under reduced pressure.

[0266] In conducting the preparation process c) the aimed compounds ofthe general formula (I), in case that Q represents group (Q-3) can beobtained, for example, by reacting 1 mole of a compound of the generalformula (III) with 1 to 1.5 moles of hydroxylamine hydrochloride in adiluent, for example, ethanol in the presence of 1 to 1.5 moles ofsodium acetate.

[0267] The reaction of the above-mentioned preparation process d) can beconducted in an appropriate diluent. As examples of such diluents usedin that case there can be mentioned water; aliphatic, alicyclic andaromatic hydrocarbons (which may optionally be chlorinated), forexample, benzene, toluene, xylene, dichloromethane, chloroform, carbontetrachloride or 1,2-dichloroethane; ethers, for example, ethyl ether,dioxane, dimethoxyethane (DME) or tetrahydrofuran (THF); nitriles, forexample, acetonitrile; alcohols, for example, methanol, ethanol orisopropanol; esters, for example, ethyl acetate; acid amides, forexample, dimethylformamide (DMF).

[0268] The preparation process d) can be conducted in the presence of abase. As a base employable in that case there can be mentioned, asinorganic bases, hydroxides, carbonates etc. of alkali metals andalkaline earth metals, for example, sodium carbonate, potassiumcarbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide orcalcium hydroxide; and as organic bases, alcoholates, tertiary amines,dialkylaminoanilines and pyridines, for example, triethylamine,1,1,4,4-tetramethyl-ethylenediamine (TMEDA) or 4-dimethylaminopyridine(DMAP).

[0269] The preparation process d) can be conducted in a substantiallywide range of temperatures. Suitable temperatures are in the range ofgenerally about −10 to about 100° C., preferably about 0 to about 50° C.Said reaction is, conducted desirably under normal pressure. Optionally,however, it is possible to conduct it under elevated pressure or underreduced pressure.

[0270] In conducting the preparation process d) the aimed compounds ofthe aforementioned general formula (I), in case Q represents group(Q-4), can be obtained, for example, by opening the ring of 1 mole of acompound of the general formula (Ib) in a diluent, for example,dichloromethane in the presence of 1 to 3 moles of triethylamine.

[0271] In conducting the preparation process a) the compounds of thegeneral formula (I) can be obtained by starting from a compound of thegeneral formula (VI) and continuously reacting without isolating thecompounds of the general formula (IV) and the compounds of the generalformula (II). And in the preparation process b) the compounds of thegeneral formula (I) can be also obtained by starting from a compound ofthe general formula (VI) and continuously reacting without isolating thecompounds of the general formula (IV) and the compounds of the generalformula (II). In conducting the preparation process c) the compounds ofthe general formula (I) can be obtained by starting from a compounds ofthe general formula (IV) and continuously reacting without isolating thecompounds of the general formula (XV) to obtain the compound of thegeneral formula (XIII), and then by starting from a compounds of thegeneral formula (XIII) and continuously reacting without isolating thecompounds of the general formula (III).

[0272] The active compounds of the aforementioned general formula (I),according to the present invention, show, as shown in the biologicaltest examples to be described later, excellent herbicidal activitiesagainst various weeds and can be used as herbicides. In the presentspecification weeds mean, in the broadest sense, all plants which growin locations where they are undesired.

[0273] The compounds of the present invention act as total or selectiveherbicides depending upon the applied concentration. The activecompounds, according to the present invention, can be used, for example,between the following weeds and cultures.

[0274] Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium,Stellaria, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca,Xanthium, Ipomoea, Polygonum, Ambrosia, Cirsium, Sonchus, Solanum,Rorippa, Lamium, Veronica, Datura, Viola, Galeopsis, Papaver, Centaurea,Galinsoga, Rotala, Lindernia etc.

[0275] Dicotyledon cultures of the genera: Gossypium, Glycine, Beta,Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita etc.

[0276] Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Eleusine, Lolium, Bromus, Avena,Cyperus, Sorghum, Agropyron, Monochoria, Fimbristylis, Sagittaria,Eleocharis, Scirpus, Paspalum, Ischaemum, Agrostis, Alopecurus, Cynodonetc.

[0277] Monocotyledon cultures of the genera: Oryza, Zea, Triticum,Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus,Allium etc.

[0278] The use of the compounds, according to the present invention, isnot restricted to the above-mentioned plants, but may be applied toother plants in the same manner. The active compounds, according to thepresent invention, can, depending upon the applied concentration,non-selectively control weeds and may be used, for example, onindustrial terrain, rail tracks, paths, places with or without treeplantings. Moreover, the active compounds, according to the presentinvention, can be used for controlling weeds in perennial cultures andapplied in, for example, afforestations, decorative tree plantings,orchards, vineyards, citrus groves, nut orchards, banana plantations,coffee plantations, tea plantations, rubber plantations, oil palmplantations, cocoa plantations, soft fruit plantings, hopfields and canbe applied also for the selective controlling of weeds in annualcultures.

[0279] According to the invention all plants and plant parts can betreated. The term plants includes all plants and plant populations, suchas desired or undesired wild plants and cultivated plants (includingnaturally occurring cultivated varieties). Cultivated plants can beplant varieties that were obtained by conventional breeding andoptimizing processes or by biotechnological and genetic engineeringmethods or a combination of such processes and methods, includingtransgenic plants and including plant varieties that cannot or can beprotected by plant patents or plant variety rights. Plant parts are allparts and organs of plants occurring above or below the surface of thesoil, e.g. shoots, leaves, needles, stalks and stems, trunks, flowers,fruits and seeds as well as roots, tubers, bulbs and rhizomes. The termplants parts also includes harvested crops and propagation material,e.g. cuttings, tubers, bulbs, rhizomes, shoots and seeds.

[0280] According to the invention the plants and plants parts aretreated using the usual methods by applying the active ingredients orcompositions containing them directly to the plants or plant parts or totheir surroundings (including the soil) or storeroom, e.g. by dipping,spraying, dusting, fogging, spreading and in the case of propagationmaterial also by coating using one or multiple layers.

[0281] The active compounds, according to the present invention, can bemade into customary formulations. As such formulations there can bementioned, for example, solutions, wettable powders, emulsions,suspensions, powders, water-dispersible granules, tablets, granules,suspension-emulsion concentrates, microcapsules in polymeric substancesor jumbo formulations.

[0282] These formulations can be prepared according to per se knownmethods, for example, by mixing the active compounds with extenders,namely liquid or solid diluents or carriers, and optionally withsurface-active agents, namely emulsifiers and/or dispersants and/orfoam-forming agents.

[0283] As liquid diluents or carriers there can be mentioned, forexample, aromatic hydrocarbons (for example, xylene, toluene,alkylnaphthalene), chlorinated aromatic or chlorinated aliphatichydrocarbons (for example, chlorobenzenes, ethylene chlorides, methylenechloride), aliphatic hydrocarbons [for example, cyclohexane or paraffins(for example, mineral oil fractions)], alcohols (for example, butanol,glycol) and their ethers, esters etc., ketones (for example, acetone,methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone), stronglypolar solvents (for example, dimethylformamide, dimethyl sulphoxide) andwater. In case of using water as an extender, for example, organicsolvents can be used as auxiliary solvents.

[0284] As solid diluents or carriers there can be mentioned, forexample, ground natural minerals (for example, kaolin, clay, talc,chalk, quartz, attapulgite, montmorillonite, diatomaceous earth) orground synthetic minerals (for example, highly dispersed silicic acid,alumina, silicates). As solid carriers for granules there can bementioned, for example, crushed and fractionated rocks (for example,calcite, marble, pumice, sepiolite, dolormite), synthetic granules ofinorganic and organic meals or particles of organic material (forexample, sawdust, coconut shells, maize cobs and tobacco stalks).

[0285] As emulsifiers and/or foam-forming agents there can be mentioned,for example, nonionic and anionic emulsifiers [for example,polyoxyethylene fatty acid esters or polyoxyethylene fatty acid alcoholethers (for example, alkylaryl polyglycol ethers, alkylsulphonates,alkylsulphates, arylsulphonates)] and albumin hydrolysis products.

[0286] As dispersants there are included, for example, ligninsulphitewaste liquor and methyl cellulose.

[0287] Tackifiers may also be used in formulations (powders, granules,emulsions). As said tackifiers there can be mentioned, for example,carboxymethyl cellulose, natural and synthetic polymers (for example,gum arabic, polyvinyl alcohol, polyvinyl acetate).

[0288] Colorants may also be used. As said colorants there can bementioned inorganic pigments (for example, iron oxide, titanium oxide,Prussian Blue) and organic dyestuffs such as alizarin dyestuffs, azodyestuffs or metal phthalocyanine dyestuffs, and further trace nutrientssuch as salts of metals such as iron, manganese, boron, copper, cobalt,molybdenum, zinc.

[0289] Said formulations can contain in a range of generally 0.1 to 95%by weight, preferably 0.5 to 90% by weight of the active compounds ofthe general formula (I).

[0290] The active compounds of the general formula (I), according to thepresent invention, can be used as such or in form of their formulationfor controlling weeds. They can be used also as a mixed agent with otherknown herbicides. Such a mixed agent can be previously prepared as aform of final formulation or can be prepared by tank-mixing on occasionof the application. As a possible mixing partner in such combinationsthere can be mentioned, for example, known herbicides such assulfonylurea type herbicides for paddy field use.

[0291] Furthermore, the active compounds of the general formula (I),according to the present invention, can be mixed also with a safener andtheir application as a selective herbicide may be broadened by such amixing. As an example of such safener1-(α,α-dimethylbenzyl)-3-p-tolylurea can be mentioned.

[0292] Surprisingly, some of the combinations of the compounds accordingto the present invention with other mixing partners show synergisticeffects.

[0293] In case of using the active compounds of the general formula (I),according to the present invention, they can be directly used as such orin form of formulations such as ready-to-use solutions, emulsions,tablets, suspensions, powders, pastes, granules or used in the use formsprepared by further dilution. The active compounds, according to thepresent invention, can be applied by means of, for example, watering,spraying, atomizing or granule application.

[0294] The active compounds of the general formula (I), according to thepresent invention, can be used at any stages before and aftergermination of plants. They may also be applied to the soil beforesowing.

[0295] The application rates of the active compounds, according to thepresent invention, may be varied in a substantial range and arefundamentally different according to the nature of the desired effect.In case of herbicidal use, as the application rate there can bementioned, for example, ranges of about 0.01 to about 4 kg, preferablyabout 0.05 to about 3 kg of the active compounds per hectare.

[0296] The preparation and fields of application of the compoundsaccording to the present invention will be described more specificallyby the following examples. However, the present invention should not berestricted to them in any way.

SYNTHESIS EXAMPLE 1

[0297]

[0298]2,4-Dichloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoic acid(3.42 g) and thionylchloride (4.22 g) were added to 1,2-dichloroethane(50 ml) The mixture, after adding several drops ofN,N-dimethylformamide, was refluxed upon heating for 4 hours. Aftercooling, the solvent was distilled off to obtain crude2,4-dichloro-3-(4,5-dihydro4-methyl-5-oxo-1H-tetrazol-1-yl)benzoylchloride (3.65 g).

[0299] A dichloromethane solution of the crude2,4-dichloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoylchloride (1.10 g) was added drop by drop to the solution of1,3-cyclohexanedione (0.44 g) and triethylamine (0.43 g) indichloro-methane (8 ml) at 5° C. and the mixture was stirred at roomtemperature for 6 hours. After completion of the reaction it wasextracted with dichloromethane (150 ml), washed with dilutedhydrochloric acid and aqueous solution of sodium hydrogen carbonate andthen dried with anhydrous magnesium sulfate. The residue, obtained bydistilling off the dichloromethane, was dissolved in acetonitrile (7ml), added with triethylamine (0.43 g) and acetonecyanohydrin (18 mg)and stirred at room temperature for 8 hours. After the solvent wasdistilled off, the residue was acidified by addition of dilutedhydrochloric acid and extracted with ethyl acetate (150 ml). The organiclayer was washed with saturated salt water and dried with anhydrousmagnesium sulfate. By distilling off the ethyl acetate, the objective2-[2,4-dichloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoyl]cyclohexan-1,3-dione(0.70 g, 51% yield from2,4-dichloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoicacid) was obtained. mp 138-140° C.

SYNTHESIS EXAMPLE 2

[0300]

[0301]3-[(4-Cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2,4-dichlorobenzoicacid (5.05 g) and thionyl chloride (5.48 g) were added to1,2-dichloroethane (60 ml) and the mixture, after adding several dropsof DMF, was refluxed upon heating. After cooling, the solvent wasdistilled off to obtain crude3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2,4-dichlorobenzoylchloride (5.46 g).

[0302] A 1,2-dichloroethane solution of3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2,4-dichlorobenzoylchloride (0.70.g) was added drop by drop to the solution of1-ethyl-5-hydroxypyrazole (0.24 g) and triethylamine (0.24 g) in1,2-dichloroethane (4 ml) at 5° C. and the mixture was stirred at roomtemperature for 6 hours. After reaction it was extracted withdichloromethane (100 ml), washed with diluted hydrochloric acid andaqueous solution of sodium hydrogen carbonate and then dried withanhydrous magnesium sulfate. The residue, obtained by distilling off thesolvent, was dissolved in 1,4-dioxane (8 ml), added with potassiumcarbonate (0.38 g) and refluxed by heating for 3 hours. After thesolvent was distilled off, the residue was treated with an aqueoussolution of potassium carbonate and washed with ethyl acetate. Theaqueous layer was acidified with hydrochloric acid and extracted withethyl acetate (150 ml). The organic layer was washed with saturated saltwater and dried with anhydrous magnesium sulfate. By distilling off theethyl acetate, the objective4-{3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2,4-di-chlorobenzoyl}-5-hydroxy-1-ethylpyrazole(0.73 g, 88% yield from3-[(4-cyclo-propyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2,4-dichlorobenzoicacid) was obtained. n_(D) ²⁰: 1.5510.

SYNTHESIS EXAMPLE 3

[0303]

[0304]3-Cyclopropyl-1-{3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2,4-dichlorophenyl}propan-1,3-dione(2.64 g) was dissolved in acetic anhydride (15 ml) and the solution,after adding triethyl orthoformate (2.12 g), was refluxed for 4 hoursupon heating. The solvent was distilled off under reduced pressure andthe residue was treated with toluene, which was distilled off underreduced pressure to obtain crude3-cyclopropyl-1-{3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2,4-dichlorophenyl}-2-ethoxymethylenepropan-1,3-dione(3.23 g).

[0305] To a mixture of3-cyclopropyl-1-{3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl)-2,4-dichlorophenyl}-2-ethoxymethylenepropan-1,3-dione(3.22 g) and hydroxylamine hydrochloride (0.54 g) in ethanol (15 ml),sodium acetate (0.62 g) was added in several portions while stirring andthe mixture was stirred at room temperature for 6 hours. The solvent wasdistilled off the mixture under reduced pressure and the residue wasextracted with ethyl acetate (120 ml), washed with salt water and driedwith anhydrous magnesium sulfate. The residue, obtained by distillingoff the ethyl acetate, was purified by silica column chromatography(ethyl acetate: n-hexane=1:1) to obtain the objective5-cyclopropyl-4-{3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2,4-dichlorobenzoyl}isoxazole(2.37 g, 84% yield from3-cyclopropyl-1-{3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2,4-dichlorophenyl}propan-1,3-dione.n_(D) ²⁰ 1.5929.

SYNTHESIS EXAMPLE 4

[0306]

[0307]5-Cyclopropyl-4-{3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2,4-dichlorobenzoyl}isoxazole(1.30 g) was dissolved in dichloromethane (10 ml) and the solution,after adding triethylamine (0.50 g) drop by drop, was stirred at roomtemperature for 6 hours.

[0308] The reaction solution was acidified by adding 2N hydrochloricacid, extracted with dichloromethane (100 ml), washed with salt waterand dried with anhydrous magnesium sulfate. By distilling off thedichloromethane the objective2-cyano-3-cyclopropyl-1-{3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2,4-dichlorophenyl}propan-1,3-dione(1.30 g, quantitative yield) was obtained. mp: 129-132° C.

[0309] The compounds, obtained in the same manner as described in theabove-mentioned Synthesis Examples 1 to 4, are shown in the followingTables 1 to 3, together with the compounds synthesized in the SynthesisExamples 1 to 4.

[0310] In Tables 1, 2 and 3

[0311] Q1 represents the group

[0312] Q2 represents the group

[0313] Q3 represent the group

[0314] Q4 represent the group

[0315] Q5 represents the group

[0316] Q6 represents the group

[0317] Q7 represents the group

[0318] Q8 represents the group

[0319] Q9 represents the group

[0320] Q10 represents the group

[0321] and,

[0322] Q11 represents the group

TABLE 1

Com- Property pound (n^(D) ₂₀ or No. Y Z R² n Q mp. ° C.) 1. H H CH₃ 0Q1 1.5923 2. H H CH₃ 0 Q4 3. H H CH₃ 0 Q6 4. H H CH₃ 1 Q1 5. H H CH₃ 1Q5 6. H H CH₃ 1 Q7 7. OCH₃ H CH₃ 0 Q1 8. OCH₃ H CH₃ 1 Q1 9. Cl H CH₃ 0Q1 10. Cl H CH₃ 1 Q1 11. CH₃ H CH₃ 1 Q1 12. H F CH₃ 0 Q1 13. H F CH₃ 0Q4 14. H F CH₃ 0 Q6 15. H F CH₃ 0 Q7 16. H F CH₃ 1 Q1 17. H F CH₃ 1 Q218. H F CH₃ 1 Q4 19. H F CH₃ 1 Q5 20. H F CH₃ 1 Q7 21. H F C₂H₅ 0 Q1 22.H F C₂H₅ 0 Q8 23. H F C₂H₅ 1 Q1 24. H F C₂H₅ 1 Q3 25. H F C₂H₅ 1 Q4 26.H F C₂H₅ 1 Q6 27. H F C₂H₅ 1 Q7 28. H F n-C₃H₇ 1 Q1 29. H F n-C₃H₇ 1 Q530. H F iso-C₃H₇ 1 Q1 31. H F iso-C₃H₇ 1 Q6 32. H F

1 Q1 33. H F

1 Q7 34. H F

1 Q1 35. H F

1 Q8 36. H F

1 Q1 37. H F

1 Q1 38. H F CHF₂ 0 Q1 39. H F CHF₂ 0 Q4 40. H F CH₂CH₂CH₂F 0 Q1 41. H FCH₂CH₂CH₂F 0 Q5 42. H F CH₂CF₃ 1 Q1 43. H F CH₂CF₃ 1 Q6 44. H FCH₂CF₂CF₃ 1 Q1 45. H Cl CH₃ 0 Q1 46. H Cl CH₃ 0 Q4 47. H Cl CH₃ 0 Q6 48.H Cl CH₃ 0 Q7 49. H Cl CH₃ 1 Q1 50. H Cl CH₃ 1 Q2 51. H Cl CH₃ 1 Q4 52.H Cl CH₃ 1 Q6 53. H Cl CH₃ 1 Q8 54. H Cl C₂H₅ 0 Q1 55. H Cl C₂H₅ 0 Q756. H Cl C₂H₅ 1 Q1 57. H Cl C₂H₅ 1 Q2 58. H Cl C₂H₅ 1 Q4 59. H Cl C₂H₅ 1Q6 60. H Cl C₂H₅ 1 Q7 61. H Cl n-C₃H₇ 1 Q1 62. H Cl n-C₃H₇ 1 Q6 63. H Cliso-C₃H₇ 1 Q1 64. H Cl iso-C₃H₇ 1 Q7 65. H Cl

1 Q1 66. H Cl

1 Q8 67. H Cl

1 Q4 68. H Cl

1 Q1 69. H Cl

1 Q4 70. H Cl

1 Q1 71. H Cl

1 Q1 72. H Cl CHF₂ 0 Q1 73. H Cl CHF₂ 0 Q5 74. H Cl CH₂CH₂CH₂F 0 Q1 75.H Cl CH₂CH₂CH₂F 0 Q6 76. H Cl CH₂CF₃ 1 Q1 77. H Br CH₃ 0 Q1 78. H Br CH₃0 Q4 79. H Br CH₃ 0 Q6 80. H Br CH₃ 0 Q7 81. H Br CH₃ 1 Q1 134-141 82. HBr CH₃ 1 Q3 83. H Br CH₃ 1 Q4 84. H Br CH₃ 1 Q6 112-115 85. H Br CH₃ 1Q8 86. H Br C₂H₅ 0 Q1 87. H Br C₂H₅ 0 Q6 88. H Br C₂H₅ 1 Q1 89. H BrC₂H₅ 1 Q2 90. H Br C₂H₅ 1 Q4 91. H Br C₂H₅ 1 Q5 92. H Br C₂H₅ 1 Q8 93. HBr C₃H₇-n 1 Q1 94. H Br C₃H₇-n 1 Q7 95. H Br C₃H₇-iso 1 Q1 96. H BrC₃H₇-iso 1 Q8 97. H Br

1 Q1 98. H Br

1 Q4 99. H Br

1 Q1 100. H Br

1 Q6 101. H Br

1 Q1 102. H Br

1 Q5 103. H Br

1 Q1 104. H Br

1 Q1 105. H Br CHF₂ 0 Q1 106. H Br CHF₂ 0 Q6 107. H Br CH₂CH₂CH₂F 0 Q1108. H Br CH₂CH₂CH₂F 0 Q7 109. H Br CH₂CF₂CF₃ 1 Q1 110. H I CH₃ 0 Q1111. H I CH₃ 0 Q6 112. H I CH₃ 1 Q1 113. H I CH₃ 1 Q6 114. H CH₃ CH₃ 0Q1 115. H CH₃ CH₃ 0 Q6 116. H CF₃ CH₃ 0 Q1 117. H CF₃ CH₃ 0 Q4 118. HCF₃ CH₃ 0 Q5 119. H CF₃ CH₃ 0 Q6 120. H CF₃ CH₃ 0 Q7 121. H CF₃ CH₃ 1 Q11.5313 122. H CF₃ CH₃ 1 Q2 123. H CF₃ CH₃ 1 Q3 124. H CF₃ CH₃ 1 Q4 125.H CF₃ CH₃ 1 Q5 126. H CF₃ CH₃ 1 Q6 127. H CF₃ CH₃ 1 Q7 128. H CF₃ CH₃ 1Q8 129. H CF₃ C₂H₅ 0 Q1 130. H CF₃ C₂H₅ 0 Q8 131. H CF₃ C₂H₅ 1 Q1 132. HCF₃ C₂H₅ 1 Q3 133. H CF₃ C₂H₅ 1 Q4 134. H CF₃ C₂H₅ 1 Q6 135. H CF₃ C₂H₅1 Q7 136. H CF₃ C₃H₇-n 1 Q1 137. H CF₃ C₃H₇-n 1 Q5 138. H CF₃ C₃H₇-iso 1Q1 139. H CF₃ C₃H₇-iso 1 Q6 140. H CF₃

1 Q1 141. H CF₃

1 Q7 142. H CF₃

1 Q5 143. H CF₃

1 Q1 144. H CF₃

1 Q1 145. H CF₃

1 Q8 146. H CF₃

1 Q1 147. H CF₃

1 Q1 148. H CF₃ CHF₂ 0 Q1 149. H CF₃ CHF₂ 0 Q4 150. H CF₃ CH₂CH₂CH₂F 0Q1 151. H CF₃ CH₂CH₂CH₂F 0 Q5 152. H CF₃ CH₂CF₃ 1 Q1 153. H CF₃ CH₂CF₃ 1Q6 154. H CF₃ CH₂CF₃ 1 Q7 155. H CF₃ CH₂CF₂CF₃ 1 Q1 156. H OCH₃ CH₃ 0 Q1157. H OCH₃ CH₃ 0 Q6 158. H OCH₃ CH₃ 1 Q1 159. H OSO₂CH₃ CH₃ 0 Q1 160. HOSO₂CH₃ CH₃ 1 Q1 161. H OSO₂CH₃ CH₃ 1 Q6 162. H SCH₃ CH₃ 0 Q1 163. HSCH₃ CH₃ 1 Q1 164. H SO₂CH₃ CH₃ 0 Q1 165. H SO₂CH₃ CH₃ 1 Q1 166. HSO₂CH₃ CH₃ 1 Q6 167. H SO₂CH₃ C₂H₅ 0 Q1 168. H SO₂CH₃ C₂H₅ 1 Q1 169. HSO₂CH₃ C₂H₅ 1 Q7 170. H SO₂CH₃ C₃H₇-iso 0 Q1 171. H SO₂CH₃ C₃H₇-iso 1 Q1172. H SO₂CH₃ C₃H₇-iso 1 Q8 173. H SO₂CH₃

1 Q1 174. H SO₂CH₃

1 Q4 175. H SO₂CH₃

1 Q1 176. H NO₂ CH₃ 0 Q1 177. H NO₂ CH₃ 0 Q6 178. H NO₂ CH₃ 0 Q7 179. HNO₂ CH₃ 1 Q1 1.5855 180. H NO₂ CH₃ 1 Q5 181. H NO₂ CH₃ 1 Q6 182. H NO₂CH₃ 1 Q7 183. H NO₂ C₂H₅ 0 Q1 184. H NO₂ C₂H₅ 0 Q8 185. H NO₂ C₂H₅ 1 Q1186. H NO₂ C₂H₅ 1 Q6 187. H NO₂ C₂H₅ 1 Q7 188. H NO₂ C₃H₇-n 1 Q1 189. HNO₂ C₃H₇-n 1 Q5 190. H NO₂ C₃H₇-iso 1 Q1 191. H NO₂ C₃H₇-iso 1 Q6 192. HNO₂

1 Q1 193. H NO₂

1 Q7 194. H NO₂

1 Q8 195. H NO₂

1 Q1 196. H NO₂

1 Q1 197. H NO₂ CHF₂ 0 Q1 198. H NO₂ CHF₂ 0 Q4 199. H NO₂ CH₂CH₂CH₂F 0Q1 200. H NO₂ CH₂CF₃ 1 Q1 201. H CN CH₃ 0 Q1 202. H CN CH₃ 0 Q6 203. HCN CH₃ 1 Q1 204. H CN CH₃ 1 Q6 205. H CN C₂H₅ 0 Q1 206. H CN C₂H₅ 1 Q1207. H CN

1 Q1 208. H CN

1 Q6 209. CO₂CH₃ Cl CH₃ 1 Q1 210. CO₂CH₃ Cl CH₃ 1 Q6 211. CO₂CH₃ Cl CH₃1 Q7 212. CO₂CH₃ SCH₃ CH₃ 1 Q1 213. CO₂CH₃ SCH₃ CH₃ 1 Q6 214. CO₂CH₃SO₂CH₃ CH₃ 0 Q1 215. CO₂CH₃ SO₂CH₃ CH₃ 1 Q1 216. CO₂CH₃ SO₂CH₃ CH₃ 1 Q6217. CO₂CH₃ SO₂CH₃ CH₃ 1 Q7 218. CH₂OCH₃ Cl CH₃ 1 Q1 219. CH₂OCH₃ Cl CH₃1 Q6 220. CH₂OCH₃ Cl CH₃ 1 Q7 221. CH₂OCH₃ SCH₃ CH₃ 1 Q1 222. CH₂OCH₃SCH₃ CH₃ 1 Q6 223. CH₂OCH₃ SO₂CH₃ CH₃ 1 Q1 224. CH₂OCH₃ SO₂CH₃ CH₃ 1 Q6225. CH₂OCH₃ SO₂CH₃ CH₃ 1 Q7 226. CH₂SCH₃ Cl CH₃ 1 Q1 227. CH₂SCH₃ ClCH₃ 1 Q6 228. CH₂SCH₃ Cl CH₃ 1 Q7 229. CH₂SCH₃ SCH₃ CH₃ 1 Q1 230.CH₂SCH₃ SCH₃ CH₃ 1 Q6 231. CH₂SCH₃ SO₂CH₃ CH₃ 1 Q1 232. CH₂SCH₃ SO₂CH₃CH₃ 1 Q6 233. CH₂SCH₃ SO₂CH₃ CH₃ 1 Q7 234. H OSO₂C₂H₅ CH₃ 1 Q1 235. HOSO₂C₃H₇-n CH₃ 1 Q1 236. H OSO₂CH₃ CH₃ 1 Q6

[0323] TABLE 2

Compound Property No. X Z R³ n Q (n^(D) ₂₀ or mp. ° C.) 237. H H CH₃ 0Q1 238. H H CH₃ 0 Q5 239. H H CH₃ 0 Q6 240. H H CH₃ 1 Q1 241. H H CH₃ 1Q5 242. H H CH₃ 1 Q6 243. H F CH₃ 0 Q1 244. H Cl CH₃ 0 Q1 136-142 245. HCl CH₃ 0 Q6 246. H Cl CH₃ 1 Q1 247. H Br CH₃ 1 Q1 248. H CH₂SO₂CH₃ CH₃ 1Q1 249. Cl H CH₃ 0 Q1 amorphous 250. Br H CH₃ 0 Q1 251. OCH₃ H CH₃ 0 Q1252. OCH₃ H CH₂CH₂CH₂F 0 Q1 253. OCH₃ H CH₂CF₃ 1 Q1 254. OSO₂CH₃ H CH₃ 0Q1 255. OSO₂CH₃ H CHF₂ 0 Q1 256. OSO₂CH₃ H CH₂CF₂CF₃ 1 Q1 257. OSO₂CH₃ HCH₃ 1 Q1 258. NO₂ H CH₃ 0 Q1 259. NO₂ H CH₃ 1 Q1 260. F Cl CH₃ 0 Q1 261.F Cl CH₃ 0 Q6 262. F Cl CH₃ 1 Q1 65-70 263. F Cl CH₃ 1 Q6 264. F Cl CH₃1 Q7 265. F Cl C₂H₅ 0 Q1 266. F Cl C₂H₅ 1 Q1 267. F Cl C₂H₅ 1 Q6 268. FCl C₃H₇-n 1 Q1 269. F Cl C₃H₇-n 1 Q6 270. F Cl

1 Q1 1.5770 271. F Cl

1 Q4 amorphous 272. F Cl

1 Q6 273. F Cl

1 Q7 1.5729 274. F Cl

1 Q8 275. F Cl

1 Q1 276. F Cl

1 Q6 277. F Cl

1 Q1 amorphous 278. F Cl

1 Q6 279. F Cl

1 Q7 147-149 280. F Cl CHF₂ 0 Q1 281. F Cl CH₂CH₂CH₂F 0 Q1 282. Cl ClCH₃ 0 Q1 138-140 283. Cl Cl CH₃ 0 Q2 284. Cl Cl CH₃ 0 Q4 285. Cl Cl CH₃0 Q6 286. Cl Cl CH₃ 0 Q7 amorphous 287. Cl Cl CH₃ 0 Q8 67-69 288. Cl ClCH₃ 1 Q1 163-165 289. Cl Cl CH₃ 1 Q3 290. Cl Cl CH₃ 1 Q4 291. Cl Cl CH₃1 Q5 292. Cl Cl CH₃ 1 Q6 293. Cl Cl CH₃ 1 Q7 amorphous 294. Cl Cl CH₃ 1Q8 129-132 295. Cl Cl C₂H₅ 0 Q1 296. Cl Cl C₂H₅ 0 Q4 297. Cl Cl C₂H₅ 0Q6 298. Cl Cl C₂H₅ 0 Q7 299. Cl Cl C₂H₅ 0 Q8 300. Cl Cl C₂H₅ 1 Q1 301.Cl Cl C₂H₅ 1 Q3 302. Cl Cl C₂H₅ 1 Q4 303. Cl Cl C₂H₅ 1 Q5 304. Cl ClC₂H₅ 1 Q6 305. Cl Cl C₂H₅ 1 Q7 306. Cl Cl C₃H₇-n 0 Q1 307. Cl Cl C₃H₇-n0 Q6 308. Cl Cl C₃H₇-n 1 Q1 309. Cl Cl C₃H₇-n 1 Q6 310. Cl Cl C₃H₇-iso 0Q1 311. Cl Cl C₃H₇-iso 0 Q6 312. Cl Cl C₃H₇-iso 1 Q1 313. Cl Cl C₃H₇-iso1 Q6 314. Cl Cl

1 Q1 1.5932 315. Cl Cl

1 Q2 316. Cl Cl

1 Q4 amorphous 317. Cl Cl

1 Q6 318. Cl Cl

1 Q1 319. Cl Cl

1 Q4 320. Cl Cl

1 Q5 321. Cl Cl

1 Q6 1.5510 322. Cl Cl

1 Q7 1.5929 323. Cl Cl

1 Q8 amorphous 324. Cl Cl

1 Q1 325. Cl Cl

1 Q6 326. Cl Cl

1 Q1 327. Cl Cl

1 Q6 328. Cl Cl

1 Q1 329. Cl Cl CHF₂ 0 Q1 330. Cl Cl CHF₂ 0 Q4 331. Cl Cl CHF₂ 0 Q6 332.Cl Cl CHF₂ 0 Q7 333. Cl Cl CH₂CH₂CH₂F 0 Q1 1.5870 334. Cl Cl CH₂CH₂CH₂F0 Q4 335. Cl Cl CH₂CH₂CH₂F 0 Q6 336. Cl Cl CH₂CH₂CH₂F 0 Q7 337. Cl ClCH₂CF₃ 1 Q1 338. Cl Cl CH₂CF₃ 1 Q5 339. Cl Cl CH₂CF₂CF₃ 1 Q1 340. Cl ClCH₂CF₂CF₃ 1 Q7 341. Cl OCH₃ CH₃ 1 Q1 342. Cl OCH₃ CH₃ 1 Q6 343. Cl OCH₃CH₃ 1 Q7 344. Cl OCH₃ C₂H₅ 1 Q1 345. Cl OCH₃

1 Q1 346. Cl SCH₃ CH₃ 1 Q1 347. Cl SCH₃ CH₃ 1 Q6 348. Cl SCH₃ CH₃ 1 Q7349. Cl SCH₃ C₂H₅ 1 Q1 350. Cl SCH₃

1 Q1 351. Cl SO₂CH₃ CH₃ 0 Q1 352. Cl SO₂CH₃ CH₃ 0 Q2 353. Cl SO₂CH₃ CH₃0 Q4 354. Cl SO₂CH₃ CH₃ 0 Q6 355. Cl SO₂CH₃ CH₃ 0 Q7 356. Cl SO₂CH₃ CH₃0 Q8 357. Cl SO₂CH₃ CH₃ 1 Q1 358. Cl SO₂CH₃ CH₃ 1 Q2 359. Cl SO₂CH₃ CH₃1 Q3 360. Cl SO₂CH₃ CH₃ 1 Q4 361. Cl SO₂CH₃ CH₃ 1 Q5 362. Cl SO₂CH₃ CH₃1 Q6 363. Cl SO₂CH₃ CH₃ 1 Q7 364. Cl SO₂CH₃ CH₃ 1 Q8 365. Cl SO₂CH₃ C₂H₅0 Q1 366. Cl SO₂CH₃ C₂H₅ 0 Q4 367. Cl SO₂CH₃ C₂H₅ 0 Q6 368. Cl SO₂CH₃C₂H₅ 0 Q7 369. Cl SO₂CH₃ C₂H₅ 0 Q8 370. Cl SO₂CH₃ C₂H₅ 1 Q1 371. ClSO₂CH₃ C₂H₅ 1 Q3 372. Cl SO₂CH₃ C₂H₅ 1 Q4 373. Cl SO₂CH₃ C₂H₅ 1 Q5 374.Cl SO₂CH₃ C₂H₅ 1 Q6 375. Cl SO₂CH₃ C₂H₅ 1 Q7 376. Cl SO₂CH₃ C₃H₇-n 0 Q1377. Cl SO₂CH₃ C₃H₇-n 0 Q6 378. Cl SO₂CH₃ C₃H₇-n 1 Q1 379. Cl SO₂CH₃C₃H₇-n 1 Q6 380. Cl SO₂CH₃ C₃H₇-iso 0 Q1 381. Cl SO₂CH₃ C₃H₇-iso 0 Q6382. Cl SO₂CH₃ C₃H₇-iso 1 Q1 383. Cl SO₂CH₃ C₃H₇-iso 1 Q6 384. Cl SO₂CH₃

1 Q1 385. Cl SO₂CH₃

1 Q2 386. Cl SO₂CH₃

1 Q4 387. Cl SO₂CH₃

1 Q5 388. Cl SO₂CH₃

1 Q6 389. Cl SO₂CH₃

1 Q7 390. Cl SO₂CH₃

1 Q8 391. Cl SO₂CH₃

1 Q4 392. Cl SO₂CH₃

1 Q5 393. Cl SO₂CH₃

1 Q1 394. Cl SO₂CH₃

1 Q6 395. Cl SO₂CH₃

1 Q1 396. Cl SO₂CH₃

1 Q6 397. Cl SO₂CH₃

1 Q1 398. Cl SO₂CH₃ CHF₂ 0 Q1 399. Cl SO₂CH₃ CHF₂ 0 Q4 400. Cl SO₂CH₃CHF₂ 0 Q6 401. Cl SO₂CH₃ CHF₂ 0 Q7 402. Cl SO₂CH₃ CH₂CH₂CH₂F 0 Q1 403.Cl SO₂CH₃ CH₂CH₂CH₂F 0 Q4 404. Cl SO₂CH₃ CH₂CH₂CH₂F 0 Q6 405. Cl SO₂CH₃CH₂CH₂CH₂F 0 Q7 406. Cl SO₂CH₃ CH₂CF₃ 1 Q1 407. Cl SO₂CH₃ CH₂CF₃ 1 Q7408. Cl SO₂CH₃ CH₂CF₂CF₃ 1 Q1 409. Cl SO₂CH₃ CH₂CF₂CF₃ 1 Q6 410. CH₃SO₂CH₃ CH₃ 0 Q1 411. CH₃ SO₂CH₃ CH₃ 0 Q6 412. CH₃ SO₂CH₃ CH₃ 0 Q7 413.CH₃ SO₂CH₃ CH₃ 1 Q1 414. CH₃ SO₂CH₃ CH₃ 1 Q3 415. CH₃ SO₂CH₃ CH₃ 1 Q4416. CH₃ SO₂CH₃ CH₃ 1 Q5 417. CH₃ SO₂CH₃ CH₃ 1 Q6 418. CH₃ SO₂CH₃ CH₃ 1Q7 419. CH₃ SO₂CH₃ CH₃ 1 Q8 420. CH₃ SO₂CH₃ C₂H₅ 0 Q1 421. CH₃ SO₂CH₃C₂H₅ 0 Q4 422. CH₃ SO₂CH₃ C₂H₅ 1 Q1 423. CH₃ SO₂CH₃ C₂H₅ 1 Q3 424. CH₃SO₂CH₃ C₂H₅ 1 Q4 425. CH₃ SO₂CH₃ C₂H₅ 1 Q5 426. CH₃ SO₂CH₃ C₂H₅ 1 Q6427. CH₃ SO₂CH₃ C₂H₅ 1 Q7 428. CH₃ SO₂CH₃ C₃H₇-n 0 Q1 429. CH₃ SO₂CH₃C₃H₇-n 1 Q1 430. CH₃ SO₂CH₃ C₃H₇-n 1 Q6 431. CH₃ SO₂CH₃ C₃H₇-iso 0 Q1432. CH₃ SO₂CH₃ C₃H₇-iso 1 Q1 433. CH₃ SO₂CH₃ C₃H₇-iso 1 Q6 434. CH₃SO₂CH₃

1 Q1 435. CH₃ SO₂CH₃

1 Q2 436. CH₃ SO₂CH₃

1 Q4 437. CH₃ SO₂CH₃

1 Q5 438. CH₃ SO₂CH₃

1 Q6 439. CH₃ SO₂CH₃

1 Q7 440. CH₃ SO₂CH₃

1 Q8 441. CH₃ SO₂CH₃

1 Q1 442. CH₃ SO₂CH₃

1 Q1 443. CH₃ SO₂CH₃

1 Q1 444. CH₃ SO₂CH₃ CHF₂ 0 Q1 445. CH₃ SO₂CH₃ CH₂CH₂CH₂F 0 Q1 446. CH₃SO₂CH₃ CH₂CF₃ 1 Q4 447. CH₃ SO₂CH₃ CH₂CF₂CF₃ 1 Q1 448. SCH₃ Cl CH₃ 0 Q166-73 449. SCH₃ Cl CH₃ 0 Q2 450. SCH₃ Cl CH₃ 0 Q4 451. SCH₃ Cl CH₃ 0 Q5452. SCH₃ Cl CH₃ 0 Q6 236-240 453. SCH₃ Cl CH₃ 0 Q7 454. SCH₃ Cl CH₃ 0Q8 455. SCH₃ Cl CH₃ 1 Q1 172-175 456. SCH₃ Cl CH₃ 1 Q3 457. SCH₃ Cl CH₃1 Q4 458. SCH₃ Cl CH₃ 1 Q5 459. SCH₃ Cl CH₃ 1 Q6 460. SCH₃ Cl CH₃ 1 Q7461. SCH₃ Cl CH₃ 1 Q8 462. SCH₃ Cl C₂H₅ 0 Q1 463. SCH₃ Cl C₂H₅ 0 Q4 464.SCH₃ Cl C₂H₅ 0 Q6 465. SCH₃ Cl C₂H₅ 0 Q7 466. SCH₃ Cl C₂H₅ 0 Q8 467.SCH₃ Cl C₂H₅ 1 Q1 468. SCH₃ Cl C₂H₅ 1 Q3 469. SCH₃ Cl C₂H₅ 1 Q4 470.SCH₃ Cl C₂H₅ 1 Q5 471. SCH₃ Cl C₂H₅ 1 Q6 472. SCH₃ Cl C₂H₅ 1 Q7 473.SCH₃ Cl C₃H₇-n 0 Q1 474. SCH₃ Cl C₃H₇-n 0 Q6 475. SCH₃ Cl C₃H₇-n 1 Q1476. SCH₃ Cl C₃H₇-n 1 Q6 477. SCH₃ Cl C₃H₇-iso 0 Q1 478. SCH₃ ClC₃H₇-iso 0 Q6 479. SCH₃ Cl C₃H₇-iso 1 Q1 480. SCH₃ Cl C₃H₇-iso 1 Q4 481.SCH₃ Cl C₃H₇-iso 1 Q6 482. SCH₃ Cl

1 Q1 483. SCH₃ Cl

1 Q2 484. SCH₃ Cl

1 Q4 485. SCH₃ Cl

1 Q5 486. SCH₃ Cl

1 Q6 487. SCH₃ Cl

1 Q7 488. SCH₃ Cl

1 Q8 489. SCH₃ Cl

1 Q1 490. SCH₃ Cl

1 Q6 491. SCH₃ Cl

1 Q1 492. SCH₃ Cl

1 Q6 493. SCH₃ Cl

1 Q1 494. SCH₃ Cl CHF₂ 0 Q1 495. SCH₃ Cl CHF₂ 0 Q6 496. SCH₃ Cl CHF₂ 0Q7 497. SCH₃ Cl CH₂CH₂CH₂F 0 Q1 498. SCH₃ Cl CH₂CH₂CH₂F 0 Q4 499. SCH₃Cl CH₂CH₂CH₂F 0 Q6 500. SCH₃ Cl CH₂CH₂CH₂F 0 Q7 501. SCH₃ Cl CH₂CF₃ 1 Q1502. SCH₃ Cl CH₂CF₂CF₃ 1 Q4 503. SCH₃ SCH₃ CH₃ 0 Q1 504. SCH₃ SCH₃ CH₃ 0Q3 505. SCH₃ SCH₃ CH₃ 0 Q4 506. SCH₃ SCH₃ CH₃ 0 Q5 507. SCH₃ SCH₃ CH₃ 0Q6 508. SCH₃ SCH₃ CH₃ 0 Q7 509. SCH₃ SCH₃ CH₃ 0 Q8 510. SCH₃ SCH₃ CH₃ 1Q1 134-141 511. SCH₃ SCH₃ CH₃ 1 Q2 512. SCH₃ SCH₃ CH₃ 1 Q4 513. SCH₃SCH₃ CH₃ 1 Q5 514. SCH₃ SCH₃ CH₃ 1 Q6 515. SCH₃ SCH₃ CH₃ 1 Q7 516. SCH₃SCH₃ CH₃ 1 Q8 517. SCH₃ SCH₃ C₂H₅ 0 Q1 518. SCH₃ SCH₃ C₂H₅ 0 Q4 519.SCH₃ SCH₃ C₂H₅ 0 Q5 520. SCH₃ SCH₃ C₂H₅ 0 Q6 521. SCH₃ SCH₃ C₂H₅ 0 Q7522. SCH₃ SCH₃ C₂H₅ 1 Q1 523. SCH₃ SCH₃ C₂H₅ 1 Q3 524. SCH₃ SCH₃ C₂H₅ 1Q4 525. SCH₃ SCH₃ C₂H₅ 1 Q6 526. SCH₃ SCH₃ C₂H₅ 1 Q7 527. SCH₃ SCH₃ C₂H₅1 Q8 528. SCH₃ SCH₃ C₃H₇-n 0 Q1 529. SCH₃ SCH₃ C₃H₇-n 0 Q6 530. SCH₃SCH₃ C₃H₇-n 1 Q1 531. SCH₃ SCH₃ C₃H₇-n 1 Q6 532. SCH₃ SCH₃ C₃H₇-iso 0 Q1533. SCH₃ SCH₃ C₃H₇-iso 0 Q6 534. SCH₃ SCH₃ C₃H₇-iso 1 Q1 535. SCH₃ SCH₃C₃H₇-iso 1 Q4 536. SCH₃ SCH₃ C₃H₇-iso 1 Q6 537. SCH₃ SCH₃

1 Q1 538. SCH₃ SCH₃

1 Q2 539. SCH₃ SCH₃

1 Q4 540. SCH₃ SCH₃

1 Q5 541. SCH₃ SCH₃

1 Q6 542. SCH₃ SCH₃

1 Q7 543. SCH₃ SCH₃

1 Q8 544. SCH₃ SCH₃

1 Q1 545. SCH₃ SCH₃

1 Q6 546. SCH₃ SCH₃

1 Q1 547. SCH₃ SCH₃

1 Q1 548. SCH₃ SCH₃ CHF₂ 0 Q1 549. SCH₃ SCH₃ CH₂CH₂CH₂F 0 Q1 550. SCH₃SCH₃ CH₂CF₃ 1 Q6 551. SCH₃ SCH₃ CH₂CF₂CF₃ 1 Q7 552. SO₂CH₃ Cl CH₃ 0 Q1amorphous 553. SO₂CH₃ Cl CH₃ 0 Q2 554. SO₂CH₃ Cl CH₃ 0 Q4 555. SO₂CH₃ ClCH₃ 0 Q5 556. SO₂CH₃ Cl CH₃ 0 Q6 84-91 557. SO₂CH₃ Cl CH₃ 0 Q7 558.SO₂CH₃ Cl CH₃ 0 Q8 559. SO₂CH₃ Cl CH₃ 1 Q1 135-137 560. SO₂CH₃ Cl CH₃ 1Q3 561. SO₂CH₃ Cl CH₃ 1 Q4 562. SO₂CH₃ Cl CH₃ 1 Q5 563. SO₂CH₃ Cl CH₃ 1Q6 109-117 564. SO₂CH₃ Cl CH₃ 1 Q7 81-83 565. SO₂CH₃ Cl CH₃ 1 Q8 566.SO₂CH₃ Cl C₂H₅ 0 Q1 567. SO₂CH₃ Cl C₂H₅ 0 Q4 568. SO₂CH₃ Cl C₂H₅ 0 Q6569. SO₂CH₃ Cl C₂H₅ 0 Q7 570. SO₂CH₃ Cl C₂H₅ 0 Q8 571. SO₂CH₃ Cl C₂H₅ 1Q1 572. SO₂CH₃ Cl C₂H₅ 1 Q2 573. SO₂CH₃ Cl C₂H₅ 1 Q4 574. SO₂CH₃ Cl C₂H₅1 Q5 575. SO₂CH₃ Cl C₂H₅ 1 Q6 576. SO₂CH₃ Cl C₂H₅ 1 Q7 577. SO₂CH₃ ClC₃H₇-n 0 Q1 578. SO₂CH₃ Cl C₃H₇-n 0 Q6 579. SO₂CH₃ Cl C₃H₇-n 1 Q1 580.SO₂CH₃ Cl C₃H₇-n 1 Q6 581. SO₂CH₃ Cl C₃H₇-iso 0 Q1 582. SO₂CH₃ ClC₃H₇-iso 0 Q6 583. SO₂CH₃ Cl C₃H₇-iso 1 Q1 584. SO₂CH₃ Cl C₃H₇-iso 1 Q4585. SO₂CH₃ Cl C₃H₇-iso 1 Q6 586. SO₂CH₃ Cl

1 Q1 587. SO₂CH₃ Cl

1 Q3 588. SO₂CH₃ Cl

1 Q4 589. SO₂CH₃ Cl

1 Q5 590. SO₂CH₃ Cl

1 Q6 591. SO₂CH₃ Cl

1 Q7 592. SO₂CH₃ Cl

1 Q8 593. SO₂CH₃ Cl

1 Q1 594. SO₂CH₃ Cl

1 Q6 595. SO₂CH₃ Cl

1 Q1 596. SO₂CH₃ Cl

1 Q1 597. SO₂CH₃ Cl CHF₂ 0 Q1 598. SO₂CH₃ Cl CH₂CH₂CH₂F 0 Q1 599. SO₂CH₃Cl CH₂CF₃ 1 Q1 600. SO₂CH₃ Cl CH₂CF₂CF₃ 1 Q1 601. SO₂CH₃ SO₂CH₃ CH₃ 0 Q1602. SO₂CH₃ SO₂CH₃ CH₃ 0 Q3 603. SO₂CH₃ SO₂CH₃ CH₃ 0 Q4 604. SO₂CH₃SO₂CH₃ CH₃ 0 Q5 605. SO₂CH₃ SO₂CH₃ CH₃ 0 Q6 606. SO₂CH₃ SO₂CH₃ CH₃ 0 Q7607. SO₂CH₃ SO₂CH₃ CH₃ 0 Q8 608. SO₂CH₃ SO₂CH₃ CH₃ 1 Q1 609. SO₂CH₃SO₂CH₃ CH₃ 1 Q2 610. SO₂CH₃ SO₂CH₃ CH₃ 1 Q4 611. SO₂CH₃ SO₂CH₃ CH₃ 1 Q5612. SO₂CH₃ SO₂CH₃ CH₃ 1 Q6 613. SO₂CH₃ SO₂CH₃ CH₃ 1 Q7 614. SO₂CH₃SO₂CH₃ CH₃ 1 Q8 615. SO₂CH₃ SO₂CH₃ C₂H₅ 0 Q1 616. SO₂CH₃ SO₂CH₃ C₂H₅ 0Q4 617. SO₂CH₃ SO₂CH₃ C₂H₅ 0 Q6 618. SO₂CH₃ SO₂CH₃ C₂H₅ 0 Q7 619. SO₂CH₃SO₂CH₃ C₂H₅ 1 Q1 620. SO₂CH₃ SO₂CH₃ C₂H₅ 1 Q3 621. SO₂CH₃ SO₂CH₃ C₂H₅ 1Q6 622. SO₂CH₃ SO₂CH₃ C₂H₅ 1 Q7 623. SO₂CH₃ SO₂CH₃ C₂H₅ 1 Q8 624. SO₂CH₃SO₂CH₃ C₃H₇-n 0 Q1 625. SO₂CH₃ SO₂CH₃ C₃H₇-n 0 Q6 626. SO₂CH₃ SO₂CH₃C₃H₇-n 1 Q1 627. SO₂CH₃ SO₂CH₃ C₃H₇-n 1 Q6 628. SO₂CH₃ SO₂CH₃ C₃H₇-iso 0Q1 629. SO₂CH₃ SO₂CH₃ C₃H₇-iso 0 Q6 630. SO₂CH₃ SO₂CH₃ C₃H₇-iso 1 Q1631. SO₂CH₃ SO₂CH₃ C₃H₇-iso 1 Q4 632. SO₂CH₃ SO₂CH₃ C₃H₇-iso 1 Q6 633.SO₂CH₃ SO₂CH₃

1 Q1 634. SO₂CH₃ SO₂CH₃

1 Q2 635. SO₂CH₃ SO₂CH₃

1 Q4 636. SO₂CH₃ SO₂CH₃

1 Q5 637. SO₂CH₃ SO₂CH₃

1 Q6 638. SO₂CH₃ SO₂CH₃

1 Q7 639. SO₂CH₃ SO₂CH₃

1 Q8 640. SO₂CH₃ SO₂CH₃

1 Q1 641. SO₂CH₃ SO₂CH₃

1 Q6 642. SO₂CH₃ SO₂CH₃

1 Q1 643. SO₂CH₃ SO₂CH₃

1 Q1 644. SO₂CH₃ SO₂CH₃ CHF₂ 0 Q1 645. SO₂CH₃ SO₂CH₃ CH₂CH₂CH₂F 0 Q1646. Cl Cl C₄H₉-n 0 Q1 647. Cl Cl C₄H₉-tet 1 Q1 648. Cl Cl C₄H₉-tert 1Q6 649. Cl Cl C₅H₁₁-n 0 Q5 650. Cl Cl C₅H₁₁-n 1 Q6 651. Cl Cl

1 Q1 652. Cl Cl

1 Q1 653. Cl Cl

1 Q5 654. Cl Cl

1 Q6 655. Cl Cl

1 Q6 656. Cl Cl CH₃ 1 Q9 657. Cl Cl CH₃ 1 Q10 658. Cl Cl CH₃ 1 Q11 659.Cl SO₂CH₃ C₅H₁₁-n 1 Q1 660. Cl SO₂CH₃ C₄H₉-tert 1 Q1 661. Cl SO₂CH₃C₄H₉-tert 1 Q6 662. Cl SO₂CH₃

1 Q1 663. Cl SO₂CH₃

1 Q1 664. Cl SO₂CH₃

1 Q5 665. Cl SO₂CH₃

1 Q6 666. Cl SO₂CH₃

1 Q1 667. Cl SO₂CH₃ CH₃ 1 Q9 668. Cl SO₂CH₃ CH₃ 1 Q10 669. Cl SO₂CH₃ CH₃1 Q11 670. Cl SO₂C₂H₅ CH₃ 1 Q1 671. Cl SO₂C₂H₅ CH₃ 1 Q6 672. ClSO₂C₃H₇-n CH₃ 1 Q1 673. SC₂H₅ Cl CH₃ 0 Q1 674. SC₂H₅ Cl CH₃ 0 Q6 675.SC₂H₅ Cl CH₃ 1 Q1 676. SC₃H₇-n Cl CH₃ 0 Q1 677. SO₂C₂H₅ Cl CH₃ 0 Q1 678.SO₂C₃H₇-n Cl CH₃ 1 Q1  678a Br Br CH₃ 1 Q1 67-68  678b Br Br C₂H₅ 1 Q1 678c Br Br

1 Q1  678d Br SO₂CH₃ CH₃ 1 Q1  96-102  678e Br SO₂CH₃ CH₃ 1 Q4 678f BrSO₂CH₃ C₂H₅ 1 Q1  678g Br SO₂CH₃

1 Q1 134-135  678h Br SO₂CH₃

1 Q4 678i OCH₃ Cl CH₃ 1 Q1 678j OCH₃ Cl C₂H₅ 1 Q1  678k OCH₃ Cl

1 Q1

[0324] TABLE 3

Compound Property No. X Y R² n Q (n₂₀ ^(D) or mp. ° C.) 679. H H CH₃ 0Q1 680. H H CH₃ 0 Q4 681. H H CH₃ 0 Q6 682. H H CH₃ 1 Q1 683. H H CH₃ 1Q5 684. H H CH₃ 1 Q7 685. H CH₃ CH₃ 0 Q1 686. H CH₃ CH₃ 0 Q6 687. H OCH₃CH₃ 0 Q1 54-59 688. H OCH₃ CH₃ 1 Q1 689. H NO₂ CH₃ 0 Q1 690. H NO₂ CH₃ 1Q1 691. F H CH₃ 0 Q1 692. F H CH₃ 0 Q4 693. F H CH₃ 0 Q6 694. F H CH₃ 1Q1 695. F H CH₃ 1 Q5 696. F H CH₃ 1 Q7 697. F H C₂H₅ 0 Q1 698. F HC₃H₇-n 1 Q1 699. F H C₃H₇-iso 0 Q1 700. F H C₃H₇-iso 1 Q1 701. F H

1 Q1 702. F H

1 Q6 703. F H

1 Q1 704. F H CHF₂ 0 Q1 705. Cl H CH₃ 0 Q1 178-179 706. Cl H CH₃ 0 Q4707. Cl H CH₃ 0 Q5 708. Cl H CH₃ 0 Q6 709. Cl H CH₃ 0 Q7 154-157 710. ClH CH₃ 0 Q8 174-176 711. Cl H CH₃ 1 Q1 712. Cl H CH₃ 1 Q2 713. Cl H CH₃ 1Q4 714. Cl H CH₃ 1 Q6 715. Cl H CH₃ I Q5 716. Cl H C₂H₅ 0 Q1 717. Cl HC₂H₅ 0 Q2 718. Cl H C₂H₅ 0 Q4 719. Cl H C₂H₅ 0 Q6 720. Cl H C₂H₅ 0 Q7721. Cl H C₂H₅ 1 Q1 722. Cl H C₂H₅ 1 Q7 723. Cl H C₃H₇-n 0 Q1 724. Cl HC₃H₇-n 0 Q6 725. Cl H C₃H₇-n 1 Q1 726. Cl H C₃H₇-n 1 Q6 727. Cl HC₃H₇-iso 0 Q1 728. Cl H C₃H₇-iso 0 Q7 729. Cl H C₃H₇-iso 1 Q1 730. Cl H

1 Q1 731. Cl H

1 Q6 732. Cl H

1 Q8 733. Cl H

1 Q1 734. Cl H

1 Q4 735. Cl H

1 Q1 736. Cl H

1 Q1 737. Cl H CHF₂ 0 Q1 738. Cl H CHF₂ 0 Q5 739. Cl H CH₂CH₂CH₂F 0 Q1740. Cl H CH₂CF₃ 1 Q1 741. Br H CH₃ 0 Q1 742. Br H CH₃ 0 Q2 743. Br HCH₃ 0 Q4 744. Br H CH₃ 0 Q5 745. Br H CH₃ 0 Q6 746. Br H CH₃ 0 Q7 747.Br H CH₃ 0 Q8 748. Br H CH₃ 1 Q1 749. Br H CH₃ 1 Q4 750. Br H CH₃ 1 Q6751. Br H CH₃ 1 Q8 752. Br H C₂H₅ 0 Q1 753. Br H C₂H₅ 0 Q3 754. Br HC₂H₅ 0 Q4 755. Br H C₂H₅ 0 Q5 756. Br H C₂H₅ 0 Q8 757. Br H C₂H₅ 1 Q1758. Br H C₂H₅ 1 Q6 759. Br H C₃H₇-n 0 Q1 760. Br H C₃H₇-n 0 Q6 761. BrH C₃H₇-n 1 Q1 762. Br H C₃H₇-n 1 Q6 763. Br H C₃H₇-iso 0 Q1 764. Br HC₃H₇-iso 0 Q6 765. Br H C₃H₇-iso 1 Q1 766. Br H

1 Q1 767. Br H

1 Q6 768. Br H

1 Q8 769. Br H

1 Q1 770. Br H

1 Q1 771. Br H

1 Q1 772. Br H CHF₂ 0 Q1 773. Br H CHF₂ 0 Q6 774. Br H CH₂CH₂CH₂F 0 Q1775. Br H CH₂CF₂CF₃ 1 Q1 776. I H CH₃ 0 Q1 777. I H CH₃ 0 Q6 778. I HCH₃ 0 Q7 779. I H CH₃ 1 Q1 780. I H C₂H₅ 0 Q1 781. I H

1 Q1 782. CH₃ H CH₃ 0 Q1 783. CH₃ H CH₃ 0 Q6 784. CH₃ H C₂H₅ 0 Q1 785.OCH₃ H CH₃ 0 Q1 786. OCH₃ H CH₃ 0 Q2 787. OCH₃ H CH₃ 0 Q4 788. OCH₃ HCH₃ 0 Q5 789. OCH₃ H CH₃ 0 Q6 790. OCH₃ H CH₃ 0 Q7 791. OCH₃ H CH₃ 0 Q8792. OCH₃ H CH₃ 1 Q1 793. OCH₃ H CH₃ 1 Q4 794. OCH₃ H CH₃ 1 Q5 795. OCH₃H CH₃ 1 Q6 796. OCH₃ H CH₃ 1 Q7 797. OCH₃ H C₂H₅ 0 Q1 798. OCH₃ H C₂H₅ 0Q3 799. OCH₃ H C₂H₅ 0 Q4 800. OCH₃ H C₂H₅ 0 Q6 801. OCH₃ H C₂H₅ 0 Q7802. OCH₃ H C₂H₅ 1 Q1 803. OCH₃ H C₂H₅ 1 Q5 804. OCH₃ H C₂H₅ 1 Q7 805.OCH₃ H C₃H₇-n 0 Q1 806. OCH₃ H C₃H₇-n 0 Q6 807. OCH₃ H C₃H₇-n I Q1 808.OCH₃ H C₃H₇-n 1 Q6 809. OCH₃ H C₃H₇-iso 0 Q1 810. OCH₃ H C₃H₇-iso 0 Q6811. OCH₃ H C₃H₇-iso 1 Q1 812. OCH₃ H

1 Q1 813. OCH₃ H

1 Q6 814. OCH₃ H

1 Q7 815. OCH₃ H

1 Q1 816. OCH₃ H

1 Q1 817. OCH₃ H

1 Q1 1.5964 818. OCH₃ H CHF₂ 0 Q1 819. OCH₃ H CHF₂ 0 Q6 820. OCH₃ HCH₂CH₂CH₂F 0 Q1 821. OCH₃ H CH₂CF₃ 1 Q1 822. OSO₂CH₃ H CH₃ 0 Q1 823.OSO₂CH₃ H CH₃ 0 Q3 824. OSO₂CH₃ H CH₃ 0 Q4 825. OSO₂CH₃ H CH₃ 0 Q5 826.OSO₂CH₃ H CH₃ 0 Q6 827. OSO₂CH₃ H CH₃ 0 Q7 828. OSO₂CH₃ H CH₃ 0 Q8 829.OSO₂CH₃ H CH₃ 1 Q1 830. OSO₂CH₃ H CH₃ 1 Q4 831. OSO₂CH₃ H CH₃ 1 Q5 832.OSO₂CH₃ H CH₃ 1 Q6 833. OSO₂CH₃ H CH₃ 1 Q7 834: OSO₂CH₃ H CH₃ 1 Q8 835.OSO₂CH₃ H C₂H₅ 0 Q1 836. OSO₂CH₃ H C₂H₅ 0 Q4 837. OSO₂CH₃ H C₂H₅ 0 Q5838. OSO₂CH₃ H C₂H₅ 0 Q6 839. OSO₂CH₃ H C₂H₅ 0 Q7 840. OSO₂CH₃ H C₂H₅ 1Q1 841. OSO₂CH₃ H C₂H₅ 1 Q6 842. OSO₂CH₃ H C₂H₅ 1 Q7 843. OSO₂CH₃ HC₃H₇-n 0 Q1 844. OSO₂CH₃ H C₃H₇-n 0 Q6 845. OSO₂CH₃ H C₃H₇-n I Q1 846.OSO₂CH₃ H C₃H₇-n 1 Q6 847. OSO₂CH₃ H C₃H₇-iso 0 Q1 848. OSO₂CH₃ HC₃H₇-iso 0 Q6 849. OSO₂CH₃ H C₃H₇-iso 1 Q1 850. OSO₂CH₃ H

1 Q1 851. OSO₂CH₃ H

1 Q6 852. OSO₂CH₃ H

1 Q7 853. OSO₂CH₃ H

1 Q1 854. OSO₂CH₃ H

1 Q1 855. OSO₂CH₃ H

1 Q1 856. OSO₂CH₃ H CHF₂ 0 Q1 857. OSO₂CH₃ H CHF₂ 0 Q4 858. OSO₂CH₃ HCH₂CH₂CH₂F 0 Q1 859. OSO₂CH₃ H CH₂CF₂CF₃ 1 Q1 860. SCH₃ H CH₃ 0 Q1 861.SCH₃ H CH₃ 0 Q2 862. SCH₃ H CH₃ 0 Q4 863. SCH₃ H CH₃ 0 Q5 864. SCH₃ HCH₃ 0 Q6 865. SCH₃ H CH₃ 0 Q7 866. SCH₃ H CH₃ 0 Q8 867. SCH₃ H CH₃ 1 Q1868. SCH₃ H CH₃ 1 Q4 869. SCH₃ H CH₃ 1 Q5 870. SCH₃ H CH₃ 1 Q6 871. SCH₃H CH₃ 1 Q7 872. SCH₃ H C₂H₅ 0 Q1 873. SCH₃ H C₂H₅ 0 Q6 874. SCH₃ H C₂H₅0 Q7 875. SCH₃ H C₂H₅ 1 Q1 876. SCH₃ H C₂H₅ 1 Q5 877. SCH₃ H C₂H₅ 1 Q7878. SCH₃ H C₃H₇-n 0 Q1 879. SCH₃ H C₃H₇-n 0 Q6 880. SCH₃ H C₃H₇-n 1 Q1881. SCH₃ H C₃H₇-iso 0 Q1 882. SCH₃ H C₃H₇-iso 1 Q1 883. SCH₃ H

1 Q1 884. SCH₃ H

1 Q6 885. SCH₃ H

1 Q1 886. SCH₃ H CHF₂ 0 Q6 887. SCH₃ H CH₂CH₂CH₂F 0 Q1 888. SO₂CH₃ H CH₃0 Q1 889. SO₂CH₃ H CH₃ 0 Q2 890. SO₂CH₃ H CH₃ 0 Q4 891. SO₂CH₃ H CH₃ 0Q5 892. SO₂CH₃ H CH₃ 0 Q6 893. SO₂CH₃ H CH₃ 0 Q7 894. SO₂CH₃ H CH₃ 0 Q8895. SO₂CH₃ H CH₃ 1 Q1 896. SO₂CH₃ H CH₃ 1 Q4 897. SO₂CH₃ H CH₃ 1 Q5898. SO₂CH₃ H CH₃ 1 Q6 899. SO₂CH₃ H CH₃ 1 Q7 900. SO₂CH₃ H CH₃ 1 Q8901. SO₂CH₃ H C₂H₅ 0 Q1 902. SO₂CH₃ H C₂H₅ 0 Q6 903. SO₂CH₃ H C₂H₅ 0 Q7904. SO₂CH₃ H C₂H₅ 1 Q1 905. SO₂CH₃ H C₂H₅ 1 Q5 906. SO₂CH₃ H C₂H₅ 1 Q7907. SO₂CH₃ H C₃H₇-n 0 Q1 908. SO₂CH₃ H C₃H₇-n 0 Q6 909. SO₂GH3 H C₃H₇-n1 QL 910. SO₂CH₃ H C₃H₇-iso 0 Q1 911. SO₂CH₃ H C₃H₇-iso 0 Q6 912. SO₂CH₃H C₃H₇-iso 1 Q1 913. SO₂CH₃ H

1 Q1 914. SO₂CH₃ H

1 Q6 915. SO₂CH₃ H

1 Q1 916. SO₂CH₃ H CHF₂ 0 Q1 917. SO₂CH₃ H CH₂CH₂CH₂F 0 Q6 918. NO₂ HCH₃ 0 Q1 919. NO₂ H CH₃ 0 Q2 920. NO₂ H CH₃ 0 Q3 921. NO₂ H CH₃ 0 Q4922. NO₂ H CH₃ 0 Q5 923. NO₂ H CH₃ 0 Q6 924. NO₂ H CH₃ 0 Q7 925. NO₂ HCH₃ 0 Q8 926. NO₂ H CH₃ 1 Q1 927. NO₂ H CH₃ 1 Q2 928. NO₂ H CH₃ 1 Q3929. NO₂ W CH₃ 1 Q4 930. NO₂ H CH₃ 1 Q6 931. NO₂ H CH₃ 1 Q8 932. NO₂ HC₂H₅ 0 Q1 933. NO₂ H C₂H₅ 0 Q2 934. NO₂ H C₂H₅ 0 Q4 935. NO₂ H C₂H₅ 0 Q6936. NO₂ H C₂H₅ 0 Q7 937. NO₂ H C₂H₅ 1 Q1 938. NO₂ H C₂H₅ 1 Q4 939. NO₂H C₂H₅ 1 Q6 940. NO₂ H C₂H₅ 1 Q7 941. NO₂ H C₃H₇-n 0 Q1 942. NO₂ HC₃H₇-n 0 Q6 943. NO₂ H C₃H₇-n 0 Q7 944. NO₂ H C₃H₇-n 1 Q1 945. NO₂ HC₃H₇-n 1 Q6 946. NO₂ H C₃H₇-iso 0 Q1 947. NO₂ H C₃H₇-iso 0 Q6 948. NO₂ HC₃H₇-iso 0 Q7 949. NO₂ H C₃H₇-iso 1 Q1 950. NO₂ H

1 Q1 951. NO₂ H

1 Q6 952. NO₂ H

1 QS 953. NO₂ H

1 Q1 954. NO₂ H

1 Q6 955. NO₂ H

1 Q1 956. NO₂ H

1 Q1 957. NO₂ H CHF₂ 0 Q1 958. NO₂ H CHF₂ 0 Q6 959. NO₂ H CH₂CH₂CH₂F 0Q1 960. NO₂ H CH₂CF₃ 1 Q1 961. NO₂ H CH₂CF₂CF₃ 1 Q1 962. CN H CH₃ 0 Q1963. CN H CH₃ 0 Q2 964. CN H CH₃ 0 Q4 965. CN H CH₃ 0 Q5 966. CN H CH₃ 0Q6 967. CN H CH₃ 0 Q7 968. CN H CH₃ 0 Q5 969. CN H CH₃ 1 Q1 970. CN HCH₃ 1 Q3 971. CN H CH₃ 1 Q4 972. CN H CH₃ 1 Q6 973. CN H CH₃ 1 Q8 974.CN H C₂H₅ 0 Q1 975. CN H C₂H₅ 0 Q6 976. CN H C₂H₅ 0 Q7 977. CN H C₂H₅ 1Q1 978. CN H C₂H₅ 1 Q6 979. CN H C₂H₅ I Q7 980. CN H C₃H₇-n 0 Q1 981. CNH C₃H₇-n 0 Q6 982. CN H C₃H₇-n 0 Q7 983. CN H C₃H₇-n 1 Q1 984. CN HC₃H₇-n 1 Q6 985. CN H C₃H₇-iso 0 Q1 986. CN H C₃H₇-iso 0 Q7 987. CN HC₃H₇-iso 1 Q1 988. CN H

1 Q1 989. CN H

1 Q6 990. CN H

1 Q1 991. CN H

1 Q1 992. CN H CHF₂ 0 Q1 993. CN H CH₂CH₂CH₂F 0 Q1 994. Cl CO₂CH₃ CH₃ 0Q1 995. Cl CO₂CH₃ CH₃ 1 Q1 996. Cl CO₂CH₃ CH₃ 1 Q6 997. Cl CO₂CH₃ CH₃ 1Q7 998. Cl CH₂OCH₃ CH₃ 1 Q1 999. Cl CH₂OCH₃ CH₃ 1 Q6 1000. Cl CH₂OCH₃CH₃ 1 Q7 1001. Cl CH₂SCH₃ CH₃ 1 Q1 1002. Cl CH₂SCH₃ CH₃ 1 Q6 1003. ClCH₂SCH₃ CH₃ 1 Q7 1004. SCH₃ CO₂CH₃ CH₃ 1 Q1 1005. SCH₃ CO₂CH₃ CH₃ 1 Q61006. SCH₃ CH₂OCH₃ CH₃ 1 Q1 1007. SCH₃ CH₂OCH₃ CH₃ 1 Q6 1008. SCH₃CH₂SCH₃ CH₃ 1 Q1 1009. SCH₃ CH₂SCH₃ CH₃ 1 Q6 1010. SO₂CH₃ CO₂CH₃ CH₃ 0Q1 1011. SO₂CH₃ CO₂CH₃ CH₃ 1 Q1 1012. SO₂CH₃ CO₂CH₃ CH₃ 1 Q6 1013.SO₂CH₃ CO₂CH₃ CH₃ 1 Q7 1014. SO₂CH₃ CH₂OCH₃ CH₃ 1 Q1 1015. SO₂CH₃CH₂OCH₃ CH₃ 1 Q6 1016. SO₂CH₃ CH₂OCH₃ CH₃ 1 Q7 1017. SO₂CH₃ CH₂SCH₃ CH₃1 Q1 1018. SO₂CH₃ CH₂SCH₃ CH₃ 1 Q6 1019. SO₂CH₃ CH₂SCH₃ CH₃ 1 Q7 1020.C₂H₅ H CH₃ 0 Q1 1021. C₂H₅ H CH₃ 0 Q6 1022. OC₂H₅ H CH₃ 1 Q1 1023. OC₂H₅H CH₃ 1 Q6

SYNTHESIS EXAMPLE 5

[0325]

[0326] Magnesium (0.18 g) and t-butyl 3-cyclopropyl-3-oxopropionate(1.36 g) were suspended in methanol (16 ml). Then carbon tetrachloride(0.6 ml) was added in small amounts and the mixture stirred for 2 hours.Methanol was distilled off the mixture under reduced pressure and theresidue was added with toluene. The toluene was distilled off underreduced pressure to completely eliminate methanol. The residue wasdissolved in toluene (40 ml), to which3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2,4-dichlorobenzoylchloride (2.57 g) was added. The mixture was stirred at room temperaturefor 6 hours and left standing for a night. It was acidified by additionof 3N HCl, extracted with ethyl acetate (100 ml) and dried withanhydrous magnesium sulfate.

[0327] Then the residue, obtained by distilling off the ethyl acetate,was dissolved in toluene (40 ml), to which 4-toluenesulfonic acidmonohydrate (0.24 g) was added and refluxed for 4 hours upon heating.After cooling, it was extracted with ethyl acetate (150 ml), washed withan aqueous solution of sodium hydrogen carbonate and salt water, anddried with anhydrous magnesium sulfate. The residue, obtained bydistilling off of ethyl acetate, was purified by silica columnchromatography (ethyl acetate: n-hexane=2:1) to obtain the objective3-cyclopropyl-1-{3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2,4-dichlorophenyl)propan-1,3-dione (2.69 g, 70% yield from3-[(4-cyclopropyl-4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2,4-dichlorobenzoicacid). n_(D) ²⁰: 1.5972.

SYNTHESIS EXAMPLE 6

[0328]

[0329] To a solution of methyl2,4-dichloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoate(4.10 g) in dioxane (70 ml), 10N sodium hydroxide (2.0 ml) and water (4ml) were added and the mixture was stirred at 60° C. for 1.5 hours.After concentrating under reduced pressure and the addition of water (50ml), an aqueous solution of sodium hydroxide was added and washed withethyl acetate (150 ml). The aqueous layer was acidified withhydrochloric acid and extracted with ethyl acetate. The organic layerwas washed with saturated salt water and dried with anhydrous magnesiumsulfate. By distilling off of ethyl acetate, the objective2,4-dichloro-3-(4,5-dihydro4-methyl-5-oxo-1H-tetrazol-1-yl)benzoic acid(3.42 g, yield 87%) was obtained. mp: 221-225° C.

SYNTHESIS EXAMPLE 7

[0330]

[0331] Methyl2,4-dichloro-3-(4,5-dihydro-5-oxo-1H-tetrazol-1-yl)benzoate (4.00 g),methyl iodide (2.36 g) and potassium carbonate (2.29 g) were suspendedin N,N-dimethylformamide (30 ml) and stirred at 60° C. After reaction,cold water was added to the reaction mixture and the mixture wasextracted with ethyl acetate (150 ml) and dried with anhydrous magnesiumsulfate. By distilling off the ethyl acetate, the objective methyl2,4-dichloro-3-(4,5-dihydro-4-methyl-5-oxo-1H-tetrazol-1-yl)benzoate(4.13 g, yield 98%) was obtained. mp: 135-137° C.

SYNTHESIS EXAMPLE 8

[0332]

[0333] To a solution of trichloromethyl chloroformate (13.41 g) intoluene (150 ml), a toluene solution of methyl3-amino-2,4-dichlorobenzoate (14.9 g) was added drop by drop undercooling with ice and the solution was refluxed for about 4 hours uponheating. After completion of the reaction the mixture of the residue(obtained by distilling off the toluene from the reaction mixture) andtrimethylsilyl azide (11.09 g) was treated with a few drops of borontrifluoride etherate and stirred at 140° C. for 21 hours. Aftercompletion of the reaction the excess of triethylsilyl azide wasdistilled off and the residue was terated with methanol (10 ml) andstirred. The mixture was added with an aqueous solution of sodiumhydroxide and washed with ethyl acetate (500 ml).

[0334] The aqueous layer was acidified with hydrochloric acid andextracted with ethyl acetate. The organic layer was washed withsaturated salt water and dried with anhydrous magnesium sulfate. Bydistilling off the ethyl acetate, the objective methyl2,4-dichloro-3-(4,5-dihydro-5-oxo-1H-tetrazol-1-yl)benzoate (yield 32%)was obtained. mp: 192-193° C.

SYNTHESIS EXAMPLE 9

[0335]

[0336] 1-Cyclopropyl-5(4H)-tetrazolinone (2.53 g) and potassiumcarbonate (3.03 g) were suspended in DMF (40 ml), to which methyl3-bromomethyl-2,4-dichlorobenzoate (5.45 g) in N,N-dimethylformamide (10ml) was added drop by drop at 5° C. and the mixture was stirred at roomtemperature for 6 hours. After completion of the reaction the mixturewas added with cold water, extracted with ethyl acetate (100 ml) anddried with anhydrous magnesium sulfate. By distilling off the ethylacetate, the objective methyl3-[(4-cyclopropyl4,5-dihydro-5-oxo-1H-tetrazol-1-yl)methyl]-2,4-dichlorobenzoate(5.28 g, yield 84%) was obtained. mp: 99-100° C.

Test Example 1 Test for Herbicidal Effect Against Paddy Field Weeds

[0337] Preparation of formulation of the active compound

[0338] Carrier: Acetone 5 parts by weight

[0339] Emulsifier: Benzyloxypolyglycolether 1 part by weight

[0340] A formulation of the active compound is obtained as an emulsionby mixing 1 part by weight of the active compound with theabove-mentioned amount of carrier and emulsifier. A prescribed amount ofsaid formulation is diluted with water to prepare a solution fortesting.

[0341] Test Method

[0342] In a greenhouse 3 seedlings of paddy rice (cultivar: Nipponbare)of 2.5 leafstage (15 cm tall) were transplanted in a 500 cm² pot filledwith paddy field soil. Then seeds of barnyard grass, smallflower,bulrush, monochoria and broad-leaved weeds (common false pimpernel,Indian toothcup, long stemmed water wort, Ammaniia multiflora Roxb.,Dopatrium junceum Hammilt etc.) were sown and water was poured on thesoil to a depth of about 2-3 cm.

[0343] 5 days after the rice transplantation a formulation of eachactive compound prepared according to the aforementioned preparationmethod was applied to the surface of the water. A water depth of 3 cmwas maintained. The herbicidal effect was examined after 3 weeks fromthe treatment. The herbicidal effect was rated as 100% in the case ofcomplete death and as 0% in the case of no herbicidal effect.

[0344] As a result, the compounds of the present invention No. 270, 271and 288 showed at the chemical amount of 0.25 kg/ha sufficientherbicidal effect against paddy field weeds and showed safety to thetransplanted paddy rice.

Test Example 2 Test of Pre-Emergence Soil Treatment Against Field Weeds

[0345] Test Method

[0346] In a greenhouse, on the surface layer of 120 cm² pots filled withsoil from the fields, seeds of barnyardgrass, foxtail, common amaranthand knotweed were sown and covered with soil. The prescribed amount of asolution of active ingredients prepared in the same manner as in theabove-mentioned Test Example 1 was spread uniformly on the soil surfacelayer of each test pot. The herbicidal effect was examined on the dayafter 4 weeks from the treatment.

[0347] Results:

[0348] The compounds of the present invention No. 84, 271, 282, 321 and705 showed at the chemical amount of 2.0 kg/ha more than 90% ofherbicidal activities against objective weeds (barnyardgrass, foxtail,common amaranth and knotweed).

Test Example 3 Test of Post-Emergence Foliage Treatment Against FieldWeeds

[0349] Test Method

[0350] In a greenhouse, seeds of barnyardgrass, foxtail, common amaranthand knotweed were sown in 120 cm² pots filled with soil from the fieldsand covered with more soil. 10 days after the sowing and soil coverage(weeds were 2-leafstage in average) the prescribed amount of a solutionof the active ingredients prepared in the same manner as in theabove-mentioned Test Example 1 was spread uniformly on the foliage ofthe test plants in each test pot. The herbicidal effect was examined onthe day after 3 weeks from the treatment.

[0351] Results:

[0352] The compounds of the present invention No. 84, 121, 270, 271,288, 455, 510, 552 and 705 showed at the chemical amount of 2.0 kg/ha90% of herbicidal activities against barnyardgrass, foxtail, commonamaranth and knotweed.

Formulation Example 1 (Granule)

[0353] To a mixture of 5 parts by weight of compound No. 271, 10 partsby weight of bentonite (montmorillonite), 58 parts by weight of talc and2 parts by weight of ligninsulphonate, 25 parts by weight of water wereadded. The mixture is well kneaded, made into granules of 10-40 mesh byextrusion granulation and dried at 40-50° C. to obtain granules.

Formulation Example 2 (Granule)

[0354] 95 parts by weight of clay mineral particles having a particlesize distribution of 0.2-2 mm are put in a rotary mixer. While rotatingit, 5 parts by weight of the compound No. 705 are sprayed together witha liquid diluent into the mixer, wetted uniformly and dried at 40-50° C.to obtain granules.

Formulation Example 3 (Emulsifiable Concentrate)

[0355] 30 parts by weight of the compound No. 282, 5 parts by weight ofxylene, 8 parts by weight of polyoxyethylenealkyl phenyl ether and 7parts by weight of calcium alkylbenzenesulphonate are mixed and stirredto obtain an emulsion.

Formulation Example 4 (Wettable Powder)

[0356] 15 parts by weight of the compound No. 84, 80 parts by weight ofa mixture of white carbon (hydrous amorphous silicon oxide fineparticles) and powder clay (1:5), 2 parts by weight of sodiumalkylbenzenesulphonate and 3 parts by weight of sodiumalkylnaphthalenesulphonate-formalin-polymer are mixed in powder form andmade into a wettable powder.

Formulation Example 5 (Water Dispersible Granule)

[0357] 20 parts by weight of the compound No. 270, 30 parts by weight ofsodium ligninsulphonate, 15 parts by weight of bentonite and 35 parts byweight of calcined diatomaceous earth powder are well mixed, added withwater, then extruded using a 0.3 mm screen and dried to obtain a waterdispersible granule.

1. A tetrazolinone derivative of the general formula (1)

wherein R¹ represents halogen, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy,C₁₋₄ alkylthio, C₁₋₄ alkylsulfonyl, C₁₋₄ alkylsulfonyloxy, C₂₋₅alkoxy-carbonyl, C₂₋₆ alkoxyalkyl, C₂₋₆ alkylthioalkyl, nitro or cyano,R² represents a hydrogen atom, C₁₋₆ alkyl, C₃₋₆ cycloalkyl which may beoptionally substituted with halogen or C₁₋₃ alkyl, C₁₋₄ haloalkyl, orphenyl which may be optionally substituted with halogen, C₁₋₃ alkyl,C₁₋₃ haloalkyl or nitro, m represents 0, 1 or 2, while the two R¹substituents may be identical or different, in case m represents 2, nrepresents 0 or 1, Q represents one of the following groups

or in which R³, R⁴, R⁵, R⁶, R⁷ and R⁸ each independently represent ahydrogen atom or C₁₋₄ alkyl, and R³ and R⁸ may form an ethylene chaintogether, R⁹ represents C₁₋₄ alkyl, R¹⁰ represents C₁₋₄ alkyl or C₃₋₆cycloalkyl which may be optionally substituted with methyl.
 2. Thecompounds of the general formula (I) according to claim 1 wherein R¹represents fluoro, chloro, bromo, methyl, ethyl, C₁₋₂ haloalkyl,methoxy, ethoxy, methylthio, ethylthio, methylsulfonyl, ethylsulfonyl,methylsulfonyloxy, ethylsulfonyloxy, methoxycarbonyl, ethoxy-carbonyl,C₂₋₄ alkoxyalkyl, C₂₋₄ alkylthioalkyl, nitro or cyano, R² represents ahydrogen atom, C₁₋₄ alkyl, C₃₋₅ cycloalkyl which may be optionallysubstituted with fluoro, chloro, bromo or C₁₋₃ alkyl, C₁₋₃ haloalkyl, orphenyl which may be optionally substituted with fluoro, chloro, bromo,methyl, ethyl, difluoromethyl or trifluoromethyl, m represents 0, 1 or2, while the two R¹ substituents may be identical or different, in casem represents 2, n represents 0 or 1, Q represents one of the followinggroups

or in which R³, R⁴, R⁵, R⁶, R⁷ and R⁸ each dependently represent ahydrogen atom, methyl or ethyl, and R³ and R⁸ may form an ethylene chaintogether, R⁹ represents C₁₋₃ alkyl, R¹⁰ represents tert-butyl orcyclopropyl which may be optionally substituted with methyl.
 3. Thecompounds of the general formula (I) according to claim 1 wherein R¹represents chloro, bromo, methyl, trifluoromethyl, methoxy, methyl-thio,methylsulfonyl, methylsulfonyloxy, methoxycarbonyl, methoxy-methyl,methylthiomethyl or nitro, R² represents a hydrogen atom, methyl, ethyl,n-propyl, isopropyl, tert-butyl, cyclopropyl which may be optionallysubstituted with fluoro, chloro, methyl, ethyl or n-propyl,difluoromethyl, 2,2,2-trifluoroethyl, 3-fluoropropyl,2,2,3,3,3-pentafluoropropyl, or phenyl which may be optionallysubstituted with fluoro, chloro, methyl, difluoromethyl ortrifluoromethyl, m represents 0, 1 or 2, while two R¹ substituents maybe identical or different, in case m represents 2 n represents 0 or 1, Qrepresents one of the following groups

in which R⁹ represents methyl or ethyl, R¹⁰ represents tert-butyl,cyclopropyl or 1-methylcyclopropyl. 4) A process for the preparation ofthe compounds of the general formula (1)

wherein R¹ represents halogen, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy,C₁₋₄ alkylthio, C₁₋₄ alkylsulfonyl, C₁₋₄ alkylsulfonyloxy, C₂₋₅alkoxycarbonyl, C₂₋₆ alkoxyalkyl, C₂₋₆ alkylthioalkyl, nitro or cyano,R² represents a hydrogen atom, C₁₋₆ alkyl, C₃₋₆ cycloalkyl which may beoptionally substituted with halogen or C₁₋₃ alkyl, C₁₋₄ haloalkyl, orphenyl which may be optionally substituted with halogen, C₁₋₃ alkyl,C₁₋₃ haloalkyl or nitro, m represents 0, 1 or 2, while the two R¹substituents may be identical or different, in case m represents 2, nrepresents 0 or 1, Q represents one of the following groups

in which R³, R⁴, R⁵, R⁶, R⁷ and R⁸ each independently represent ahydrogen atom or C₁₋₄ alkyl, and R³ and Rs may form an ethylene chaintogether, R⁹ represents C₁₋₄ alkyl, R¹⁰ represents C₁₋₄ alkyl or C₃₋₆cycloalkyl which may be optionally substituted with methyl,characterized in that a) compounds of the general formula (IIa)

wherein R¹, R², m and n have the same definition as aforementioned, andT¹ represents one of the following groups

in which R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ have the same definitions asmentioned above, are reacted to a rearrangement in the presence of abase and cyanide, or b) in case that; Q represents group (O-2):compounds of the general formula (IIb)

wherein R¹, R², m and n have the same definitions as mentioned above,and T² represents one of the following groups;

in which R⁹ has the same definition as mentioned above are reacted to arearrangement in the presence of a base; or c) in case that Q representsgroup (Q-3): compounds of the general formula (III)

wherein R¹, R², R¹⁰, m and n have the same definitions as aforementionedand R¹¹ represents C₁₋₄ alkyl, preferably methyl or ethyl, are reactedwith hydroxylamine, or d) in case that Q represents group (Q-4):compounds of the general formula (Ib)

wherein R¹, R², R¹⁰, m and n have the same definitions as mentionedabove, are reacted to a ring-opening in the presence of a base.
 5. Aherbicidal composition, characterized in that it contains at least onetetrazolinone/derivative/of the general formula (I) according toclaim
 1. 6. A process for combating weeds, characterized in thattetrazolinone derivatives of the general formula (I) according to claim1 are allowed to act on the weeds and or their harbitat.
 7. Use oftetrazolinone derivatives of the general formula (I) according to claim1 for combating weeds.
 8. A process for the preparation of herbicidalcompositions, characterized in that tetrazolinone derivatives of thegeneral formula (I) according to; claim 1 are mixed with extendersand/or surface active agents.
 9. A tetrazolinone derivative representedby the general formula

wherein R¹, R², m and n have the same definition as described in any ofthe claims 1 to 3, W represents halogen, hydroxy or one of the followinggroups

in which R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ have the same definition asdescribed in any of the claims 1 to 3, and R¹¹ represents C₁₋₄ alkyl.